CN115954431B - Zinc-silver battery and method for improving efficiency of zinc-silver battery - Google Patents
Zinc-silver battery and method for improving efficiency of zinc-silver battery Download PDFInfo
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- CN115954431B CN115954431B CN202310129078.2A CN202310129078A CN115954431B CN 115954431 B CN115954431 B CN 115954431B CN 202310129078 A CN202310129078 A CN 202310129078A CN 115954431 B CN115954431 B CN 115954431B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application discloses a zinc-silver battery and a method for improving the efficiency of the zinc-silver battery, wherein the zinc-silver battery comprises a silver electrode and a zinc electrode, a conductive carbon material is used as a substrate, and an electrodeposition process is adopted to directly deposit and grow the silver electrode on the substrate; or directly depositing and growing a zinc electrode on the substrate by adopting an electrodeposition process; or respectively adopting an electrodeposition process to deposit and grow a zinc electrode and a silver electrode on different substrates. According to the application, by changing the coating mode of the electrode material in the silver-zinc battery and depositing the two-dimensional conductive material on the electrode surface, the growth of Zn dendrite is hindered, the interface resistance of the battery is effectively reduced, the cycling stability of the battery is improved, the capacity and the cycling performance of the battery are improved, and the material cost is reduced.
Description
Technical Field
The application belongs to the technical field of zinc-silver batteries, and particularly relates to a zinc-silver battery and a method for improving efficiency of the zinc-silver battery.
Background
Flexible batteries play a critical role in implementing wearable systems. Among the various energy intensive devices, a flexible silver zinc (Ag-Zn) secondary battery is one of the most promising candidate batteries, having high energy density and power density and stable output voltage. However, the low specific capacity and poor long-term cycling performance resulting from the growth of high resistance polymer binders and zinc dendrites limit the application of Ag-Zn batteries. These challenges not only hamper the widespread use of Ag-Zn batteries, but also create safety concerns.
In recent years, efforts have been made to improve the performance of ag—zn secondary batteries. Strategies to change the cell cathode and electrolyte, such as the introduction of cellophane films, optimization of electrolyte concentration and addition of two-dimensional additives, are utilized in order to increase capacity and energy density, but the performance and stability of the cell remain to be further improved. In particular, the interfacial resistance of the electrode material and the current collector is hardly reduced due to the presence of the high-resistance polymer binder. Therefore, development of a new silver-zinc battery preparation process is urgently needed to reduce the interfacial resistance of the silver-zinc battery, improve the reliability of the battery and improve the electrical performance.
Disclosure of Invention
In order to solve the technical problems, the application adopts the following technical scheme: a method for improving the efficiency of a zinc-silver battery comprises a silver electrode and a zinc electrode, wherein the silver electrode is directly deposited and grown on a substrate by adopting an electrodeposition process by taking a conductive carbon material as the substrate; or directly depositing and growing a zinc electrode on the substrate by adopting an electrodeposition process; or respectively adopting an electrodeposition process to deposit and grow a zinc electrode and a silver electrode on different substrates.
As the optimization of the technical scheme, carbon cloth is adopted as a silver electrode deposition substrate, and silver electrodes are deposited and grown on the carbon cloth; and adopting the foamy copper as a zinc electrode deposition substrate, and depositing and growing a zinc electrode on the foamy copper.
As a preferable mode of the technical proposal, the carbon cloth is used as a working electrode, the Ag foil is used as a counter electrode, and the electrolyte is 0.01-0.5M Ag + Solution, electrodeposited at room temperature with a constant voltage of-0.5V to-1V, and deposited at 0.01-2MZnCl 2 In the solution, the current density is 0.1-50mA/cm 2 Under the condition of (1) using Zn as a counter electrode, continuously using carbon cloth as a working electrode, and chloridizing the working electrode to obtain an AgCl@CC cathode;
using foamy copper as working electrode, 1cm×1cm zinc foil as counter electrode, and 0.05-0.5M ZnSO 4 ·7H 2 O is dissolved in 100mL of deionized water as electrolyte at 10m-100mA/cm 2 And (3) electrodepositing the Zn nano sheet for 10min to 3h at room temperature to obtain the Zn@CF anode.
As the optimization of the technical scheme, the conductive two-dimensional material is dispersed in an aqueous solution with the concentration of 0.05-3wt%, an AgCl@CC cathode or a Zn@CF anode is placed in the solution to serve as a working electrode by utilizing a two-electrode system, a graphite rod serves as a counter electrode, and voltage is applied to the working electrode, so that the conductive two-dimensional material is deposited on the working electrode, and a layer of conductive two-dimensional material is deposited on the AgCl@CC cathode or the Zn@CF anode.
Preferably, the conductive two-dimensional material is graphene or mxene material.
A zinc-silver battery comprises the AgCl@CC cathode, zn@CF anode, and PVA-G/ZnCl 2 The PVA or KOH gel electrolyte is assembled into a complete battery.
As a preferable mode of the technical scheme, the assembled zinc-silver battery is put into a fume hood for aging, and redundant water in the battery is removed.
The beneficial effects of the application are as follows: according to the application, the coating mode of the electrode material in the silver-zinc battery is changed, so that the use of a binder is avoided, the interface resistance of the battery is effectively reduced, the capacity and the cycle performance of the battery are improved, and the material cost is reduced. By depositing the two-dimensional conductive material on the surface of the electrode, dendrite generation is effectively inhibited, interface resistance is reduced, and the silver-zinc battery with long service life and large capacity is obtained. The electrode formed by direct electrodeposition is used as an electrode without adhesive, so that the problem of low specific capacity caused by large contact resistance in the existing silver-zinc battery is solved. The copper foam substrate is also used as a current collector for the first time to be introduced into an Ag-Zn secondary battery so as to prevent Zn dendrite growth and improve the cycle stability of the battery.
Drawings
Fig. 1 is a schematic diagram of the discharge test results of a silver-zinc battery.
Detailed Description
The following description of the present application will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
Example 1
A1 cm. Times.1 cm piece of Ag foil was used as the counter electrode, and a 1 cm. Times.1 cm piece of Carbon Cloth (CC) was used as the counter electrodeIs a working electrode, 0.1MAgNO 3 The solution serves as an electrolyte. Then at room temperature at-1V/cm 2 Is electrodeposited so that Ag micro-platelets/micro-polyhedra are electrodeposited on CC. At 0.1MZnCl 2 In the solution, the current density was 4mA/cm 2 Under the condition of using 1cm multiplied by 1cm Zn as a counter electrode, and continuously using Carbon Cloth (CC) as a working electrode, and chloridizing to obtain the AgCl@CC cathode.
The Copper Foam (CF) substrate was purified in 3% HCl solution and taken out as a working electrode. The counter electrode was a 1cm X1 cm zinc foil, and 1gH was applied 3 BO 3 、6.25gNa 2 SO 4 And 6.25g ZnSO 4 ·7H 2 O was dissolved in 50mLDI water as an electrolyte. At 40mA/cm 2 And (3) electrodepositing the Zn nano sheet for 1h at room temperature to obtain the Zn@CF anode.
Dispersing graphene serving as a conductive two-dimensional material into an aqueous solution, wherein the concentration is 1.0wt%, placing an AgCl@CC cathode into the solution by using a two-electrode system to serve as a working electrode, and applying voltage on the working electrode by using a graphite rod as a counter electrode, so that the graphene is deposited on the working electrode, and the AgCl@CC cathode with a layer of graphene conductive two-dimensional material deposited on the surface is obtained. And placing the Zn@CF anode in the graphene solution to serve as a working electrode, applying voltage on the working electrode by using a graphite rod as a counter electrode, so that graphene is deposited on the working electrode, and obtaining the Zn@CF anode with a layer of graphene conductive two-dimensional material deposited on the surface.
AgCl@CC cathode with surface deposited with a layer of graphene conductive two-dimensional material, zn@CF anode with surface deposited with a layer of graphene conductive two-dimensional material, and PVA-G/ZnCl 2 And assembling to form the zinc-silver secondary battery.
Example 2
A1 cm. Times.1 cm piece of Ag foil was used as the counter electrode, a 1 cm. Times.1 cm piece of Carbon Cloth (CC) was used as the working electrode, and 0.01MAgNO 3 The solution serves as an electrolyte. Then at room temperature at-0.5V/cm 2 Is electrodeposited so that Ag micro-platelets/micro-polyhedra are electrodeposited on CC. At 0.01MZnCl 2 In the solution, the current density was 1mA/cm 2 Under the conditions of 1cm×1cmZn is used as a counter electrode, carbon Cloth (CC) is continuously used as a working electrode, and the AgCl@CC cathode is obtained through chlorination.
The Copper Foam (CF) substrate was purified in 3% hcl solution and taken out as a working electrode. The counter electrode was a 1cm X1 cm zinc foil, and 1gH was applied 3 BO 3 、6.25gNa 2 SO 4 And 6.25g ZnSO 4 ·7H 2 O was dissolved in 50mLDI water as an electrolyte. At 10mA/cm 2 And (3) electrodepositing the Zn nano sheet for 3 hours at room temperature to obtain the Zn@CF anode.
And dispersing the mxene serving as a conductive two-dimensional material into an aqueous solution, wherein the concentration is 2.0wt%, placing an AgCl@CC cathode into the solution by using a two-electrode system to serve as a working electrode, and applying voltage on the working electrode by using a graphite rod as a counter electrode, so that the mxene is deposited on the working electrode, and the AgCl@CC cathode with a layer of mxene conductive two-dimensional material deposited on the surface is obtained. And placing the Zn@CF anode in the mxene solution to serve as a working electrode, applying voltage on the working electrode by using a graphite rod as a counter electrode, so that the mxene is deposited on the working electrode, and obtaining the Zn@CF anode with a layer of mxene conductive two-dimensional material deposited on the surface.
And assembling the AgCl@CC cathode with the surface deposited with a layer of mxene conductive two-dimensional material, the Zn@CF anode with the surface deposited with a layer of mxene conductive two-dimensional material, and KOH gel to form the zinc-silver secondary battery.
Comparative example
A conventional zinc-silver secondary battery was assembled using a zinc electrode as an anode, silver oxide as a cathode, and KOH as an electrolyte.
The zinc-silver secondary batteries of examples 1, 2 and comparative example were subjected to discharge tests, and the test results are shown in fig. 1. As can be seen from the test results shown in FIG. 1, the zinc-silver secondary battery prepared by the method for improving the efficiency of the zinc-silver battery has longer battery discharge time because the binder is avoided in the process of the method, and dendrite generation is effectively inhibited, so that the interface resistance of the battery is effectively reduced, the loss is reduced, and the efficiency of the battery is improved.
It should be noted that technical features such as electrodeposition related to the present patent application should be considered as the prior art, and specific structures, working principles, and control modes and spatial arrangements related to the technical features may be conventional in the art, and should not be considered as the application point of the present patent application, which is not further specifically described in detail herein.
While the preferred embodiments of the present application have been described in detail, it should be appreciated that numerous modifications and variations may be made in accordance with the principles of the present application by those skilled in the art without undue burden, and thus, all technical solutions which may be obtained by logic analysis, reasoning or limited experimentation based on the principles of the present application as defined by the claims are within the scope of protection as defined by the present application.
Claims (3)
1. The method for improving the efficiency of the zinc-silver battery comprises a silver electrode and a zinc electrode, and is characterized in that carbon cloth is adopted as a silver electrode deposition substrate, and a silver electrode is deposited and grown on the carbon cloth; adopting foamy copper as a zinc electrode deposition substrate, depositing and growing a zinc electrode on the foamy copper,
using carbon cloth as working electrode, ag foil as counter electrode, and 0.01-0.5M Ag electrolyte + Solution, electrodeposited at room temperature with a constant voltage of-0.5V to-1V, and deposited at 0.01-2MZnCl 2 In the solution, the current density is 0.1-50mA/cm 2 Under the condition of (1) using Zn as a counter electrode, continuously using carbon cloth as a working electrode, and chloridizing the working electrode to obtain an AgCl@CC cathode;
using foamy copper as working electrode, 1cm×1cm zinc foil as counter electrode, and 0.05-0.5M ZnSO 4 ·7H 2 O is dissolved in 100mL of deionized water as electrolyte at 10m-100mA/cm 2 Under constant current density, electrodepositing Zn nano sheet for 10min to 3h at room temperature to obtain Zn@CF anode, dispersing conductive two-dimensional material in water solution with concentration of 0.05-3wt%, using a two-electrode system, placing AgCl@CC cathode or Zn@CF anode in the solution as working electrode, using graphite rod as counter electrode, applying voltage on the working electrode to deposit conductive two-dimensional material to working electricityAnd depositing a layer of conductive two-dimensional material on the AgCl@CC cathode or the Zn@CF anode, wherein the conductive two-dimensional material is graphene or mxene.
2. A zinc-silver battery, characterized in that the AgCl@CC cathode, zn@CF anode, and PVA-G/ZnCl prepared by the method of claim 1 are prepared 2 The PVA or KOH gel electrolyte is assembled into a complete battery.
3. The zinc-silver battery of claim 2, wherein the assembled zinc-silver battery is aged in a fume hood to remove excess water from the battery and to provide the zinc-silver battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112510178A (en) * | 2020-11-27 | 2021-03-16 | 华北电力大学 | Three-dimensional alloy negative electrode material and application thereof in preparation of secondary energy storage battery |
| CN113054194A (en) * | 2021-03-15 | 2021-06-29 | 浙江大学 | Nitrogen-carbon nanotube material, preparation method thereof and application thereof in preparation of flexible zinc-manganese battery |
| CN113299928A (en) * | 2021-05-24 | 2021-08-24 | 哈尔滨工业大学 | Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material |
| CN113764741A (en) * | 2021-07-29 | 2021-12-07 | 华东师范大学 | Flexible paper-based battery and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112510178A (en) * | 2020-11-27 | 2021-03-16 | 华北电力大学 | Three-dimensional alloy negative electrode material and application thereof in preparation of secondary energy storage battery |
| CN113054194A (en) * | 2021-03-15 | 2021-06-29 | 浙江大学 | Nitrogen-carbon nanotube material, preparation method thereof and application thereof in preparation of flexible zinc-manganese battery |
| CN113299928A (en) * | 2021-05-24 | 2021-08-24 | 哈尔滨工业大学 | Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material |
| CN113764741A (en) * | 2021-07-29 | 2021-12-07 | 华东师范大学 | Flexible paper-based battery and preparation method thereof |
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