CN116072866A - Cyanation composite interface for stabilizing negative electrode of zinc-based battery and preparation method thereof - Google Patents

Cyanation composite interface for stabilizing negative electrode of zinc-based battery and preparation method thereof Download PDF

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CN116072866A
CN116072866A CN202211633433.1A CN202211633433A CN116072866A CN 116072866 A CN116072866 A CN 116072866A CN 202211633433 A CN202211633433 A CN 202211633433A CN 116072866 A CN116072866 A CN 116072866A
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zinc
negative electrode
composite interface
preparing
based battery
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罗斌
汪洋
黄靖云
叶志镇
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Wenzhou Zinc Times Energy Co ltd
Wenzhou Research Institute Of Zhejiang University
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Wenzhou Zinc Times Energy Co ltd
Wenzhou Research Institute Of Zhejiang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a cyanation composite interface for stabilizing a negative electrode of a zinc-based battery and a preparation method thereof, wherein the interface is a solid electrolyte interface rich in zinc ferrocyanide and zinc ferrocyanide. The interface may be constructed in situ by means of an electrochemical reaction. The method provided by the invention can generate a uniform and compact zinc iron cyanide/zinc iron cyanide composite interface on the surface of the zinc negative electrode, and the interface can effectively induce desolvation, prevent water in electrolyte from corroding the zinc negative electrode, realize effective protection of the zinc negative electrode of the zinc-based battery, and improve the electrochemical performance and the cycle life of the zinc-based battery.

Description

Cyanation composite interface for stabilizing negative electrode of zinc-based battery and preparation method thereof
Technical Field
The invention belongs to the technical field of energy materials, relates to a cyanation composite interface for stabilizing a zinc-based battery cathode and a preparation method thereof, can be applied to a water-based zinc-based battery, solves the problems of dendrite growth, dead zinc, parasitic reaction and the like of the zinc-based battery at present, and can effectively improve the coulomb efficiency and the cycle life of the zinc-based battery.
Background
Along with the aggravation of the consumption of non-renewable resources such as fossil energy and the like in the current international society, the energy supply and demand balance is seriously inclined, and the non-negligible potential safety hazard is brought to the long-term survival and development of people. However, the lithium ion battery widely used at present still has the fatal problems of outstanding safety problem, high raw material cost and the like, and restricts the application of the lithium ion battery in the field of large-scale energy storage. Based on the problems, zinc-based batteries become a hotspot widely paid attention to society due to the advantages of abundant zinc resources, high safety and the like, and are expected to be applied to power grid-level energy storage.
However, zinc-based batteries currently have some problems to be solved, such as: dendrite growth caused by uneven zinc deposition, hydrogen evolution corrosion caused by zinc activity, and the like. These problems severely limit the cycle life and coulombic efficiency of zinc-based batteries. In order to solve the problem, an artificial interface engineering strategy is commonly adopted at present, namely, an artificial modification layer is coated or grown on the surface of a zinc electrode, so that good induction regulation on zinc deposition is realized. In the past, the use of binders was often required for the artificially modified layer, and such ex-situ coatings had limited improvement due to tearing by the zinc coating under high capacity cycling. In addition, the existing modified layer and binder have high cost, and are not beneficial to mass production and popularization. Therefore, it is important to provide a high-efficiency low-cost mass production process to prepare a high-performance in-situ modified interface layer.
Disclosure of Invention
Aiming at the problems of zinc dendrite growth caused by uneven zinc deposition on the surface of a zinc cathode and hydrogen evolution corrosion and even passivation caused by zinc and water reaction, the invention provides a cyanation composite interface for stabilizing a zinc-based battery cathode and a preparation method thereof. The preparation method is an effective electrochemical synthesis route and can be suitable for different application scenes.
The invention adopts the technical scheme that:
a preparation method of a cyanated composite interface for stabilizing a negative electrode of a zinc-based battery adopts an electrochemical method and comprises the following steps:
dissolving a cyano-modified oxidation additive and an auxiliary stabilizer in a solvent to prepare a cyano-rich oxidizing electrolyte, wherein: the concentration of the cyano modified oxidation additive is 0.01-5 g/mL, and the concentration of the auxiliary stabilizer is 0.01-1 mol/L;
preparing a buffering agent, adding the buffering agent into the cyano-rich oxidizing electrolyte, controlling the proportion to maintain the pH of the mixed solution within the range of 0.4-7, and preserving heat at 10-25 ℃ for later use to obtain the electrolyte;
preparing polishing solution, immersing zinc foil into the polishing solution for reaction for 3 s-10 min, taking out, and cleaning with deionized water to obtain a zinc electrode;
preparing a counter electrode, wherein the surface area of the counter electrode is 1.5-3 times of that of the zinc electrode;
the zinc electrode, the counter electrode and the electrolyte form an electrolytic cell to be charged and discharged under constant current or constant voltage, and the current density range under the constant current condition is 0.1-5 mA/cm 2 The voltage range under the constant voltage condition is 0.05-0.5V, and the duration time is 20 s-10 min; and taking out the zinc electrode after the reaction, cleaning with deionized water and drying to obtain the zinc ferricyanide/zinc ferrocyanide composite interface modified zinc cathode.
In the above technical scheme, further, the cyano modified oxidation additive is one or more of ferricyanide salt and ferrous cyanide salt.
Further, the auxiliary stabilizer is one or more of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium bromide and potassium bromide, and the solvent is one or more of water, alcohols, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Further, the buffer is one or more of acetic acid, phosphoric acid, boric acid, citric acid, barbituric acid, tannic acid and salts thereof.
Further, the main components of the polishing solution are one or more of hydrochloric acid, sulfuric acid, acetic acid, formic acid and trifluoromethane sulfonic acid, and the pH is maintained at 0.5-2.
Further, the counter electrode is one or more of zinc, copper, iron, aluminum, carbon, platinum, gold and silver.
A zinc anode with zinc ferricyanide/zinc ferricyanide composite interface modification prepared by any of the methods described above.
By utilizing the preparation method provided by the invention, the zinc ferricyanide/zinc ferrocyanide composite interface with different microstructures can be formed on the surface of the zinc cathode in situ. The electronegative cyano group rich in the composite interface can effectively attract and induce zinc ions to be uniformly deposited, and plays a role in repelling solvent water to achieve the effect of preventing hydrogen evolution corrosion. Experiments prove that the composite interface remarkably stabilizes the zinc cathode, and improves the service life and the cycle stability of the zinc-based battery.
Drawings
FIG. 1 is a scanning electron microscope image of the cyanated composite interface prepared using the electrochemical method in example 1;
FIG. 2 is an elemental distribution under an energy spectrometer of a cyanated composite interface prepared using an electrochemical method in example 1;
FIG. 3 is a graph showing the cycling performance of the cyanated composite interface modified zinc anode prepared using the electrochemical method in example 1;
FIG. 4 is the cycle performance of the assembled battery of example 1 using an unmodified zinc anode;
FIG. 5 is a graph of example 2 at 5mA cm -2 -2mAh cm -2 Zinc deposition morphology of the surface of the unmodified zinc cathode under constant current charge-discharge cycle;
FIG. 6 is a 5mA cm thick cyanoned composite interface modified zinc anode prepared by electrochemical deposition in example 2 -2 -2mAh cm -2 Electrochemical performance under constant current charge-discharge cycle;
FIG. 7 is a graph of unmodified zinc anode at 5mA cm in example 2 -2 -2mAh cm -2 Electrochemical performance under constant current charge-discharge cycle.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
example 1: electrochemical preparation of Zinc ferricyanide/Zinc ferricyanide composite interface modified Zinc cathode 1) 4g Potassium ferricyanide and 10mmol sodium chloride were dissolved in 40mL deionized water using ultrasound and
stirring the magnetons to obtain a clear cyano-rich oxidizing electrolyte;
2) Adding 1mol/L acetic acid solution into the cyano-rich oxidizing electrolyte, stirring uniformly, controlling the configuration proportion to enable the pH value of the mixed solution to be 5, and preserving the temperature at the room temperature of 25 ℃ for later use;
3) Preparing hydrochloric acid solution with pH=1 as polishing solution, immersing zinc foil into the solution, polishing for 10s, and washing and drying the zinc foil by deionized water;
4) Cutting the treated zinc foil to 3x3cm 2 The size was used as working electrode, and the counter electrode was 4X4cm 2 Taking the zinc foil with the size of 2) and taking the solution to be used as electrolyte, performing constant voltage discharge operation with the voltage of 0.3V between the two electrodes for 5min, taking out the zinc foil after the reaction is finished, and washing and drying the zinc foil by deionized water;
5) The zinc foil is cut to proper size for assembling a symmetrical battery, and the electrolyte is 2MZnSO 4 The membrane is a whatman glass fiber. Assembled cell at 10mA cm -2 -2mAh cm -2 Constant current charge and discharge test is carried out under the condition.
FIG. 1 is a scanning electron microscope image of a cyanated composite interface prepared by an electrochemical method in the embodiment, wherein the zinc foil surface shown in FIG. 1 is provided with a zinc iron cyanide/zinc iron cyanide composite material with good crystallinity and is in a polyhedral cube configuration;
FIG. 2 shows the distribution of elements of the cyanated composite interface prepared by the electrochemical method in the present embodiment under an energy spectrometer, wherein the elements of zinc, iron, carbon and nitrogen are uniformly distributed on the surface of the modified zinc electrode as shown in FIG. 2, which indicates that the adopted preparation method can efficiently form a uniform zinc iron cyanide/zinc iron cyanide composite interface in situ on the surface of the zinc foil;
fig. 3 is a graph showing the cycling performance of the cyanated composite interface modified zinc anode prepared using the electrochemical method in this example. As shown in the figure, zinc-based cells using zinc ferricyanide/zinc ferricyanide composite interface modified zinc cathodes can be operated at 10mA cm -2 -2mAh cm -2 The zinc iron cyanide/zinc iron cyanide composite interface can effectively protect a zinc cathode from zinc dendrites and hydrogen evolution corrosion, and can effectively induce uniform zinc deposition.
Fig. 4 is a graph showing the cycle performance of the assembled battery using the unmodified zinc anode of the present example, and the unmodified zinc anode suffered from serious dendrite growth problems at an early stage of the cycle. Eventually after a cycle time of 150 hours, the grown zinc dendrites penetrated the separator causing cell short circuit failure.
Example 2: electrochemical preparation of zinc ferricyanide/zinc ferricyanide composite interface modified zinc cathode 1) 5g of potassium ferricyanide and 10mmol of sodium chloride are dissolved in 80mL of ethanol, and a clear cyano-rich oxidizing electrolyte is obtained by stirring with ultrasound and magnetons;
2) Adding 1.2mol/L citric acid solution into the cyano-rich oxidizing electrolyte, stirring uniformly, controlling the configuration proportion to enable the pH value of the mixed solution to be 6, and preserving the temperature at the room temperature of 25 ℃ for later use;
3) The reacted zinc foil was removed with tweezers and the possibly attached precursor solution was rinsed with deionized water and dried in an oven at 70 ℃ for 6 hours.
4) Taking out the dried zinc foil, cutting to a proper size to serve as an electrode of the zinc ion battery, and adopting 2M ZnSO 4 The solution was used as an electrolyte and whatman glass fiber was used as a separator to assemble button cells. The battery is at 5mA cm -2 -2mAh cm -2 Constant current charge and discharge test is carried out under the condition.
FIG. 5 is a graph of unmodified zinc anode at 5mA cm under the conditions of example 2 -2 -2mAh cm -2 And (5) zinc deposition morphology after the condition test cycle. As shown, a large number of disordered zinc sheets appear on the surface of the zinc cathode and intertwine with the separator fibers, and such disordered zinc deposition can exacerbate hydrogen evolution corrosion to the batteryThe stable circulation brings trouble.
FIG. 6 is a 5mA cm sample of a cyanated composite interface modified negative electrode prepared using the electrochemical deposition method in example 2 -2 -2mAh cm -2 The condition test cycle performance. The zinc iron cyanide/zinc iron cyanide composite interface modified zinc cathode prepared by using an electrochemical method can still be at 5mA cm -2 -2mAh cm -2 The zinc iron cyanide/zinc iron cyanide composite interface can effectively protect a zinc cathode from zinc dendrites and hydrogen evolution corrosion, and can effectively induce uniform zinc deposition.
Fig. 7 is a graph showing the cycling performance of the unmodified zinc anode under the test conditions of example 2. As shown, the electrochemical cycle performance of the unmodified zinc anode was poor compared to the modified interface-protected zinc anode, exhibiting higher electrochemical polarization and unstable charge-discharge cycle, and the battery was severely degraded at 170 hours due to chemical passivation.
In summary, the invention provides a cyanated composite interface for stabilizing a negative electrode of a zinc-based battery and a preparation method thereof, wherein the method comprises an electrochemical method preparation route, and can prepare a zinc iron cyanide/zinc iron cyanide composite interface with a high-crystallization microstructure. The cyano-enriched composite interface can effectively inhibit the problems of hydrogen evolution, zinc dendrite and the like of the zinc-based battery, and realizes long-time stable operation of the zinc metal cathode.

Claims (8)

1. A method for preparing a cyanated composite interface for stabilizing a negative electrode of a zinc-based battery, the method comprising the steps of:
dissolving a cyano-modified oxidation additive and an auxiliary stabilizer in a solvent to prepare a cyano-rich oxidizing electrolyte, wherein: the concentration of the cyano modified oxidation additive is 0.01-5 g/mL, and the concentration of the auxiliary stabilizer is 0.01-1 mol/L;
preparing a buffering agent, adding the buffering agent into the cyano-rich oxidizing electrolyte, controlling the proportion to maintain the pH of the mixed solution within the range of 0.4-7, and preserving heat at 10-25 ℃ for later use to obtain the electrolyte;
preparing polishing solution, immersing zinc foil into the polishing solution for reaction for 3 s-10 min, taking out, and cleaning with deionized water to obtain a zinc electrode;
preparing a counter electrode, wherein the surface area of the counter electrode is 1.5-3 times of that of the zinc electrode;
the zinc electrode, the counter electrode and the electrolyte form an electrolytic cell to be charged and discharged under constant current or constant voltage, and the current density range under the constant current condition is 0.1-5 mA/cm 2 The voltage range under the constant voltage condition is 0.05-0.5V, and the duration time is 20 s-10 min; and taking out the zinc electrode after the reaction, cleaning with deionized water and drying to obtain the zinc ferricyanide/zinc ferrocyanide composite interface modified zinc cathode.
2. The method for preparing a cyanated composite interface for stabilizing a negative electrode of a zinc-based battery according to claim 1, wherein the cyano-modified oxidation additive is one or more of ferricyanide salt and ferricyanide salt.
3. The method for preparing the cyanated composite interface for stabilizing the negative electrode of the zinc-based battery according to claim 1, wherein the auxiliary stabilizer is one or more of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium bromide and potassium bromide, and the solvent is one or more of water, alcohols, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
4. The method for preparing a cyanated composite interface for stabilizing a negative electrode of a zinc-based battery according to claim 1, wherein the buffering agent is one or more of acetic acid, phosphoric acid, boric acid, citric acid, barbituric acid, tannic acid and salts thereof.
5. The method for preparing the cyanated composite interface for stabilizing the negative electrode of the zinc-based battery according to claim 1, wherein the main component of the polishing solution is one or more of hydrochloric acid, sulfuric acid, acetic acid, formic acid and trifluoromethanesulfonic acid, and the pH is maintained at 0.5-2.
6. The method for preparing a cyanated composite interface for stabilizing a negative electrode of a zinc-based battery according to claim 1, wherein the counter electrode is one or more of zinc, copper, iron, aluminum, carbon, platinum, gold, and silver.
7. A zinc negative electrode with a zinc ferricyanide/zinc ferricyanide composite interface modification, characterized in that it is produced by the method according to any one of claims 1 to 6.
8. A zinc cell comprising the zinc anode according to claim 7.
CN202211633433.1A 2022-12-19 2022-12-19 Cyanation composite interface for stabilizing negative electrode of zinc-based battery and preparation method thereof Pending CN116072866A (en)

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