CN115763775A - Zinc cathode double-layer protective layer and preparation method thereof - Google Patents
Zinc cathode double-layer protective layer and preparation method thereof Download PDFInfo
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- CN115763775A CN115763775A CN202211503392.4A CN202211503392A CN115763775A CN 115763775 A CN115763775 A CN 115763775A CN 202211503392 A CN202211503392 A CN 202211503392A CN 115763775 A CN115763775 A CN 115763775A
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Abstract
The invention discloses a zinc cathode double-layer protective layer and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out hydrothermal treatment on the cleaned zinc metal foilObtaining a modified zinc metal foil; the original zinc metal foil is commercial zinc metal foil, and the hydrothermal treatment is carried out under the conditions of set mixed solution, set temperature and set time length. According to the invention, after hydrothermal treatment, double protective layers are constructed on the surface of the commercial zinc metal foil in situ, the upper uniform ZnO layer can play roles in isolating electrolyte and helping interfacial zinc ion transportation, and the lower CuZn layer 5 The alloy layer or the In metal layer can guide the zinc to be rapidly and uniformly deposited so as to avoid the growth of dendritic crystals, and the modified zinc metal cathode provided by the invention forms two protective layers with different functions on the surface, so that the modified zinc metal cathode shows better electrochemical reaction activity and circulation stability, and meets the requirement of simple process.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, relates to a zinc metal negative electrode material, and particularly relates to a zinc negative electrode double-layer protective layer and a preparation method thereof.
Background
In the face of depletion of fossil energy and consequent environmental degradation, development of sustainable energy and storage systems is imminent. Lithium ion batteries were the first commercial rechargeable energy storage devices, but their inherent instability has prompted the development of safer, cheaper multivalent aqueous metal batteries. Wherein, the water system zinc ion battery has the ultrahigh theoretical specific capacity (5855 mAh cm) -3 ) Lower redox potential (-0.763V vs standard hydrogen electrode, SHE), dual electron transfer mechanism and minimal environmental impact are considered promising next generation energy storage devices. In the polar aqueous electrolyte, the zinc ion is in a solvated compact ion pair [ Zn (H) 2 O) 6 ] 2+ Are present in the double electric layer, they need to overcome a large desolvation barrier to deposit on the zinc cathode, which slows the reaction kinetics.
In order to solve the serious corrosion caused by excessive contact between the zinc cathode and active water molecules, the adoption of high-concentration electrolyte (water in salt) and hydrogel electrolyte to reduce the active water molecules in the interface is an effective strategy, but the practical application is difficult to achieve due to high cost. Alternatively, it was found that the artificial SEI layer can insulate the electrolyte and uniform Zn by 2+ Flux improves the reversibility of the zinc negative electrode, and can be roughly divided into an insulating layer and a conductive layer according to its own characteristics. For insulating artificial layers such as ZnO, MOF and montmorillonite, they are generally used as physical barriers to isolate electrolytes or to provide appropriately sized pores and interlayer spaces to promote desolvation of large size solvated ion complexes, thereby inhibiting the corrosion process of zinc. However, since the inorganic layer has a relatively high rigidity, the electrode is galvanizedBreakage is likely to occur in many cases. Thus, 3D porous conductive artificial layers or scaffolds such as porous carbon and metal scaffolds have also been extensively reported, as the interconnected network structure can provide a large number of nucleation sites and uniform electric fields to guide the uniform deposition of zinc, and have sufficient free volume to accommodate the deposition of byproducts and zinc. The zinc-philic metal/alloy particles or artificial layers on the surface of the negative electrode have good capabilities of adjusting zinc deposition behaviors and inhibiting hydrogen evolution reactions, so that the zinc negative electrode has a long service life. It would be an excellent strategy to greatly increase the stability of zinc cathodes if these two artificial layers could be tightly bonded together. Furthermore, the special double-protection-layer structure can be used in electrochemical devices such as supercapacitors, sensors and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a zinc negative electrode double-layer protection layer and a preparation method thereof, and the zinc negative electrode double-layer protection layer can greatly improve the cycling stability of a zinc metal negative electrode in a water-based zinc ion battery.
In order to achieve the purpose, the technical scheme of the invention is as follows: a zinc negative electrode double-layer protection layer is formed by constructing a double-layer protection layer on the upper surface of a zinc metal foil in situ through hydrothermal treatment, and CuZn is uniformly deposited on the bottom layer 5 Layer or In layer of CuZn 5 And a ZnO layer is arranged on the layer or the In layer.
Carrying out hydrothermal treatment on clean zinc metal foil to obtain modified zinc metal; the solute of the solution used for the hydrothermal treatment is Na 2 CO 3 、Zn(Ac) 2 And Cu (Ac) 2 Or InCl 3 Any one of the above.
The temperature of the hydrothermal treatment is 25-250 ℃.
The time of the hydrothermal treatment is 0.1 to 100 hours.
The zinc cathode based on the zinc cathode double-layer protective layer is applied to an electrochemical device.
The method specifically comprises the application in zinc ion batteries, super capacitors and sensors.
When the material is applied to a zinc ion battery, the counter electrode is made of the same material as the zinc cathode or MnO 2 。
Advantageous effects
The invention greatly improves the reactivity and the cycling stability of the zinc metal cathode by constructing the double protective layers in situ, has simple process and no pollution to the environment, and has good application prospect.
Drawings
Fig. 1a is an XRD pattern of commercial and modified zinc metal anodes prepared in examples 1 and 5 of the present invention.
Fig. 1b is an XRD pattern of the modified zinc metal cathode prepared in example 4 of the present invention.
Fig. 2a is a scanning electron microscope image of the surface of a commercial zinc metal negative electrode prepared in example 1 of the present invention.
Fig. 2b is a scanning electron microscope image of the surface of the modified zinc metal negative electrode prepared in example 4 of the present invention.
Fig. 2c is a scanning electron microscope image of the modified zinc metal surface prepared in example 5 of the present invention.
Fig. 2d is a scanning electron microscope image of the cross section of the modified zinc metal anode prepared in example 5 of the present invention and the corresponding X-ray energy line scan curve. Fig. 3a is a graph of the electrochemical cycling performance of an aqueous zinc ion symmetric cell assembled with a commercial zinc metal negative electrode prepared in example 1 of the present invention.
Fig. 3b is a diagram of electrochemical cycle performance of an aqueous zinc ion symmetric battery assembled by the modified zinc metal negative electrode prepared in example 2 of the present invention.
Fig. 3c is a diagram of electrochemical cycle performance of an aqueous zinc ion symmetric cell assembled by preparing a modified zinc metal negative electrode in example 3 of the present invention.
Fig. 3d is a graph of electrochemical cycling performance of an aqueous zinc ion symmetric cell assembled with a modified zinc metal negative electrode prepared in example 5 of the present invention.
FIG. 4 shows commercial and modified zinc metal anodes and MnO prepared in examples 1 and 5 of the present invention 2 The electrochemical cycle performance diagram of the whole battery assembled into the water system zinc ion battery.
Detailed Description
The present invention is further illustrated by the following detailed embodiments to make the technical solutions and advantages of the present invention clearer, but the technical parameters in the following embodiments are not to be construed as limiting the present invention.
The invention provides a zinc cathode double-layer protective layer and a preparation method thereof, aiming at the problem that the existing zinc metal cathode material is poor in electrochemical reaction activity and cycling stability.
The invention provides a preparation method of a zinc cathode double-protection layer, which comprises the following steps of carrying out hydrothermal treatment on a zinc metal foil to obtain a modified zinc metal foil; the original zinc metal foil is a commercialized zinc metal foil, and the hydrothermal treatment is carried out in a set metal salt mixed solution at a set temperature for a set time.
The invention utilizes the ion exchange reaction of the zinc metal foil, two protective layers with different functions are constructed on the surface in situ through the hydrothermal treatment of commercial zinc metal foil, the upper uniform ZnO layer can play the roles of isolating electrolyte and helping the transportation of interface zinc ions, and the lower CuZn layer 5 The alloy layer or the In metal layer can guide the zinc to be rapidly and uniformly deposited so as to avoid the growth of dendritic crystals, thereby greatly improving the cycle stability and the reaction kinetics of the zinc cathode material and improving the electrochemical performance of the water system zinc ion battery.
The temperature in the hydrothermal treatment can fluctuate within a certain range, and the temperature fluctuation range can be up and down with a 5 ℃ difference.
In some examples of this embodiment, the hydrothermal treatment is for a time period of 0.1 to 100 hours. When the hydrothermal time is 0.5-30 h, the electrochemical reaction activity and the cycling stability of the modified zinc cathode are improved more obviously.
In some examples of this embodiment, the temperature of the hydrothermal treatment is 25 to 250 ℃. When the temperature is 50-200 ℃, the electrochemical reaction activity and the cycling stability of the modified zinc cathode are improved more obviously.
In some examples of this embodiment, the solute of the hydrothermal treatment solution is Na 2 CO 3 ，Zn(Ac) 2 Plus Cu (Ac) 2 Or InCl 3 The solvent is not limited to deionized water.
In another embodiment of the invention, a modified zinc metal anode is provided, which is obtained by the above preparation method.
In a third embodiment of the invention, there is provided a use of the above-described modified zinc metal negative electrode in an electrochemical device.
The electrochemical device comprises a zinc ion battery, a super capacitor, a sensor and the like.
In a fourth embodiment of the present invention, the modified zinc metal negative electrode is used as a negative electrode material as it is.
The ion battery of the invention is preferably a zinc ion battery. The counter electrode being itself or MnO 2 。
The modified zinc metal obtained by the preparation method can obtain better electrochemical activity and cycling stability in a symmetrical battery, and can also obtain better cycling stability and electrochemical performance after being assembled into a full battery.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1: bare Zn sample
Commercial zinc metal was sonicated in ethanol for ten minutes to clean the surface of impurities, labeled as Bare Zn. The X-ray diffraction pattern is shown in figure 1, and the prepared Bare Zn sample is a pure zinc metal phase. Scanning electron microscopy images as shown in figure 2a, surface cracks are a significant cause of dendrite growth.
The prepared Bare Zn sample is cut into a wafer with the diameter of 15mm by a slicer, and the same Bare Zn wafer or MnO is used 2 The electrolyte is 2mol/L and is used as a counter electrode to be assembled into a symmetrical battery and a full battery respectively -1 ZnSO of 4 And (3) assembling the solution into a CR2025 button cell in the air, and sealing the cell by using a sealing machine to obtain the button cell. And finally, carrying out constant-current charge and discharge test on the battery by using a blue-current charge and discharge instrument.
The negative electrode material prepared by the embodiment is used in a symmetrical battery, and the area current density is 0.5mA cm -2 And the area capacity is 0.5mAh cm -2 The charge and discharge test was carried out in a full cell at a current density of 5ag -1 Next, a charge/discharge test is performed. As shown in FIG. 3a, the symmetrical cell was charged and discharged 205h at a high overpotential of 70mV, and then a short circuit occurred. As shown in FIG. 4, the first-turn discharge capacity of the full cell was 170.1mAh g -1 And decreased to 57.01mAh g after 1990 cycles -1 。
Example 2: sample of Zn @ Zn
The Bare Zn sample obtained in example 1 was mixed with Na 2 CO 3 And Zn (AC) 2 And putting the mixed solution into a hydrothermal kettle, and treating for 3 hours at the temperature of 140 ℃ to obtain a Zn @ Zn sample.
Cleaning Zn @ Zn with deionized water and ethanol, drying at 60 deg.C, slicing into 15mm diameter slices with slicer, and processing with the same Zn @ Zn slices or MnO 2 The electrolyte is 2mol/L and is used as a counter electrode to be assembled into a symmetrical battery and a full battery respectively -1 ZnSO of 4 And filling the solution into the air to obtain a CR2025 button cell, and sealing the cell by using a sealing machine to obtain the button cell. And finally, carrying out constant-current charge and discharge test on the battery by using a blue-current charge and discharge instrument.
The cathode material prepared by the above example is used in a symmetrical battery, and the area current density is 0.5mA cm -2 And area capacity of 0.5mAh cm -2 Next, a charge/discharge test was performed. As shown in FIG. 3b, the symmetrical cell was charged and discharged at an overpotential of 30mV for 270h, which resulted in a short circuit.
Example 3: cu @ Zn sample
The Bare Zn sample obtained in example 1 was mixed with Na 2 CO 3 And Cu (AC) 2 And putting the mixed solution into a hydrothermal kettle together, and treating for 3 hours at the temperature of 140 ℃ to obtain the Cu @ Zn sample.
Cleaning Cu @ Zn with deionized water and ethanol, drying at 60 deg.C, slicing into 15mm diameter slices with slicer, and processing with the same Cu @ -Zn slices or MnO 2 The electrolyte is 2mol/L and is used as a counter electrode to be assembled into a symmetrical battery and a full battery respectively -1 ZnSO of 4 The solution is filled in the air to form a CR2025 button cell, and the cell is sealed by a sealing machineAnd sealing to obtain the button cell. And finally, performing constant-current charge and discharge test on the battery by using a blue-current charge and discharge instrument.
The cathode material prepared by the above example is used in a symmetrical battery, and the area current density is 0.5mA cm -2 And area capacity of 0.5mAh cm -2 Next, a charge/discharge test was performed. As shown in FIG. 3c, the symmetrical cell was charged and discharged with 20mV overpotential for 470h and then short-circuited.
Example 4: inZn @ Zn sample
The Bare Zn sample obtained in example 1 was mixed with Na 2 CO 3 ，Zn(AC) 2 And InCl 3 And putting the mixed solution into a hydrothermal kettle together, and treating for 3 hours at the temperature of 140 ℃ to obtain the InZn @ Zn sample. And it was confirmed by the X-ray diffraction pattern shown In fig. 1b and the scanning electron microscope image shown In fig. 2b that an In metal layer and a uniform ZnO nanorod layer were formed on the surface of the metallic zinc foil.
Cleaning InZn @ Zn with deionized water and ethanol, drying at 60 deg.C, slicing into 15mm diameter round piece with the same InZn @ Zn round piece or MnO 2 The electrolyte is 2mol/L and is used as a counter electrode to be assembled into a symmetrical battery and a full battery respectively -1 ZnSO of 4 And filling the solution in the air to obtain a CR2025 button cell, and sealing the cell by using a sealing machine to obtain the button cell. And finally, carrying out constant-current charge and discharge test on the battery by using a blue-current charge and discharge instrument.
Example 5: cuZn @ Zn sample
The Bare Zn sample obtained in example 1 was mixed with Na 2 CO 3 ，Zn(AC) 2 And Cu (Ac) 2 And putting the mixed solution into a hydrothermal kettle, and treating for 3 hours at the temperature of 140 ℃ to obtain the CuZn @ Zn sample. Scanning electron microscopy images are shown in fig. 2c, with a uniform ZnO nanorod layer on the surface. And it is proved by the X-ray diffraction pattern shown in fig. 1a and the X-ray energy spectrometer line scan shown in fig. 2d that the formed double protection layer is the ZnO nanorod layer on top, and CuZn 5 The alloy layer is under.
Cleaning CuZn @ Zn with deionized water and ethanol, drying at 60 deg.C, slicing into 15mm diameter slices with slicer, and processing with the same CuZn @ Zn slices or MnO 2 The electrolyte is 2mol/L and is used as a counter electrode to be assembled into a symmetrical battery and a full battery respectively -1 ZnSO of 4 And filling the solution into the air to obtain a CR2025 button cell, and sealing the cell by using a sealing machine to obtain the button cell. And finally, carrying out constant-current charge and discharge test on the battery by using a blue-current charge and discharge instrument.
The cathode material prepared by the above example is used in a symmetrical battery, and the area current density is 0.5mA cm -2 And area capacity of 0.5mAh cm -2 The charging and discharging tests were carried out in full cells at a current density of 5Ag -1 Next, a charge/discharge test was performed. As shown in fig. 3d, the symmetric cell was charged and discharged with a low overcharge of 16mV for 2200h or more. As shown in FIG. 4, the first-turn discharge capacity of the full cell was 188.3mAh cm -2 And after 2500 times of circulation, the concentration is reduced to 139.7mAh cm -2 。
The results show that the material prepared by the invention takes the zinc metal foil which is easy to generate ion exchange as a matrix, and takes the modified zinc metal foil which is subjected to hydrothermal treatment as the negative electrode of the zinc ion battery. It was found that ZnO nanorods in the upper layer and CuZn in the lower layer were formed after the hydrothermal treatment 5 Alloys or In metals. The formation of the two different phases and the distribution of the two phases on the surface of the zinc cathode are proved by an X-ray diffraction spectrum, a scanning electron microscope image and an X-ray energy spectrum image. Wherein, the upper ZnO layer can isolate active water molecules and improve zinc ion transmission at the interface, and the lower CuZn layer 5 The alloy layer or In metal layer can guide the uniform deposition of zinc metal. The method is a simple and effective method for improving the electrochemical performance of the negative electrode.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. Zinc cathode double layerThe protective layer is characterized in that a double-layer protective layer is constructed on the upper surface of the zinc metal foil in situ through hydrothermal treatment, and CuZn is uniformly deposited on the bottom layer 5 Layer or In layer of CuZn 5 And a ZnO layer is arranged on the layer or the In layer.
2. The method for preparing the zinc negative electrode double-layer protection layer according to claim 1, wherein the clean zinc metal foil is subjected to hydrothermal treatment to obtain modified zinc metal; the solute of the solution used for the hydrothermal treatment is Na 2 CO 3 、Zn(Ac) 2 And Cu (Ac) 2 Or InCl 3 Any one of the above.
3. The method for preparing the zinc negative electrode double-layer protection layer according to claim 2, wherein the temperature of the hydrothermal treatment is 25 to 250 ℃.
4. The method for preparing the zinc negative electrode double-layer protection layer according to claim 2, wherein the hydrothermal treatment time is 0.1 to 100 hours.
5. Use of a zinc anode based on the zinc anode bilayer protective layer of claim 1 in an electrochemical device.
6. The use according to claim 7, in particular in zinc ion batteries, supercapacitors, sensors.
7. The use of claim 7, wherein, when used in a zinc ion battery, the counter electrode is the same material as the zinc negative electrode or MnO 2 。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117542948A (en) * | 2024-01-10 | 2024-02-09 | 华北电力大学 | Water-based zinc ion battery negative electrode material, preparation method and zinc ion battery |
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| CN117542948A (en) * | 2024-01-10 | 2024-02-09 | 华北电力大学 | Water-based zinc ion battery negative electrode material, preparation method and zinc ion battery |
| CN117542948B (en) * | 2024-01-10 | 2024-03-29 | 华北电力大学 | Water-based zinc ion battery negative electrode material, preparation method and zinc ion battery |
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