CN116826193A - Electrolyte additive for aqueous zinc ion secondary battery and battery thereof - Google Patents

Electrolyte additive for aqueous zinc ion secondary battery and battery thereof Download PDF

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CN116826193A
CN116826193A CN202310967837.2A CN202310967837A CN116826193A CN 116826193 A CN116826193 A CN 116826193A CN 202310967837 A CN202310967837 A CN 202310967837A CN 116826193 A CN116826193 A CN 116826193A
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zinc
electrolyte
methylimidazole
additive
ion battery
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杨阳
张明浩
赵金保
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Xiamen University
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Xiamen University
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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
    • 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 application relates to a zinc ion battery electrolyte additive and a battery using the additive, and belongs to the technical field of zinc ion batteries. The additive is N-methylimidazole or a derivative thereof. N-methylimidazole can be adsorbed on the surface of a zinc anode through electrostatic effect, so that an interface buffer layer can be formed on one hand, the pH at the interface is stabilized, and byproducts accumulated along with the hydrogen evolution process are removed; on the other hand, the zinc ion diffusion in the 2D direction can be limited, the nucleation size of zinc deposition is reduced, the zinc deposition layer is leveled, the growth of dendrites is inhibited, and the cycle stability of the zinc cathode is obviously improved. In addition, the N-methylimidazole can also accelerate the deposition and dissolution process of the manganese oxide in the charge and discharge process, so that the capacity of the positive electrode is greatly improved.

Description

Electrolyte additive for aqueous zinc ion secondary battery and battery thereof
Technical Field
The application belongs to the technical field of zinc ion batteries, and particularly relates to a zinc ion battery electrolyte additive and application thereof.
Background
With the increasing increase of environmental pollution and the increasing exhaustion of fossil resources, renewable energy sources are receiving more and more attention. Because renewable energy sources naturally have instability, energy storage systems capable of stable output play a vital role in the utilization of renewable energy sources. However, the high risk of organic electrolytes in lithium ion batteries with the highest ratios in the energy storage market and the high cost of electrode materials currently result in limited application in large energy storage systems. To be used forZinc ion secondary battery with metallic zinc as negative electrode has low oxidation-reduction potential (-0.76V, vs. SHE) and high theoretical capacity (820 mAh g -1 ) And the aqueous electrolyte has the advantages of green safety and low cost, and is one of the new generation secondary battery systems with great potential. However, the problems of zinc metal anode side dendrite growth, hydrogen evolution, passivation of surface byproducts and the like seriously prevent commercial application of high-performance zinc ion batteries. Particularly, the continuous accumulation of basic zinc sulfate byproducts accompanied with hydrogen evolution on the surface of the electrode can generate a large number of insulating sites on the surface of the anode, so that the growth and surface passivation of dendrites are enhanced, the polarization of the battery is increased, and the failure of the battery is accelerated.
At present, researchers obtain good results by constructing a zinc-philic conductive substrate, designing an artificial interface protection layer, regulating electrolyte and the like. Among them, electrolyte adjustment by introducing additives has outstanding advantages of simplicity, high efficiency, economy, and the like, and is widely paid attention to researchers. It is worth noting that from a thermodynamic point of view, the hydrogen evolution process during zinc deposition cannot be completely avoided, while the accumulation of by-products associated with hydrogen evolution is extremely detrimental to the circulation of the zinc anode. Most of the research at the present stage is focused on inhibiting dendrite growth and hydrogen evolution, and few methods for eliminating byproducts are involved. Furthermore, the modification effect solely for dendrite growth or hydrogen evolution reaction is not ideal.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a multifunctional electrolyte buffer additive, which aims to simultaneously solve the problems of poor circulation stability of a zinc cathode and low capacity of the anode by stabilizing the pH of the interface of the zinc cathode and the electrolyte, simultaneously inhibiting dendrite growth and accelerating the deposition and dissolution process of the manganese anode.
In order to achieve the aim, the application provides an electrolyte additive for an aqueous zinc ion battery, which is imidazole and imidazole derivatives with alkyl, carboxyl, amino, nitro and halogen on side chains; it is characterized by having a pKa value between 3 and 8, being capable of reversibly binding and releasing protons under neutral conditions, and being easily adsorbed to zinc anode surfaces such as N-methylimidazole, imidazole, 2-methylimidazole, 4-methylimidazole, histamine, benzimidazole, 1-methyl-1H-imidazole-4, 5-dicarboxylic acid, 2-nitroimidazole, 4-bromo-1H-imidazole, N-butylimidazole, etc.
Most preferred is N-methylimidazole.
Preferably, the N-methylimidazole is added in an amount of 0.05M to 0.5M, most preferably 0.2M.
Preferably, the pH of the aqueous electrolyte is in the range of 3.5 to 5.2, most preferably 4.0.
Preferably, the zinc salt of the electrolyte comprises zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, zinc triflate. Most preferred is zinc sulphate.
Preferably, the concentration of zinc sulphate in the electrolyte is 1M-3M, most preferably 2M.
Preferably, the electrolyte also contains a manganese ion additive. The manganese ions can be derived from manganese nitrate, manganese sulfate and manganese chloride. Most preferred is manganese sulfate.
Preferably, the concentration of manganese ions in the electrolyte is between 0.05M and 0.5M, most preferably 0.2M.
Preferably, the negative electrode material of the zinc ion battery has zinc sheets, zinc foil, zinc powder, foam zinc, zinc rods, most preferably 0.1mm zinc foil.
Preferably, the positive electrode active material of the zinc ion battery is a manganese-based material. Comprises manganese monoxide, manganese dioxide, zinc manganate, lithium manganate, manganous oxide and polyaniline intercalated manganese dioxide. Most preferred is polyaniline intercalated manganese dioxide.
Preferably, the separator of the zinc ion battery is selected from glass fiber, polyethylene, polypropylene, mixed cellulose. Most preferably glass fibers.
The application has the beneficial effects that:
1. the N-methylimidazole or the derivative additive thereof in the electrolyte provided by the application can be adsorbed on the surface of a zinc anode through electrostatic action. The ability of the N-methylimidazole to reversibly bind to release protons can rapidly remove basic zinc sulfate byproducts accumulated on the surface of the zinc anode. The adsorption effect thereof makes the buffer effect be closer to the generation site of the byproducts, thereby continuously keeping the fresh state of the surface of the zinc cathode.
2. N-methylimidazole adsorbed on the surface of the zinc cathode can limit the diffusion of zinc ions in the 2D direction in the deposition process through electrostatic shielding effect, and reduce the nucleation size of zinc deposition, so that a zinc deposition layer is leveled, and the growth of dendrites is inhibited.
The rapid proton transport kinetics between the N-methylimidazole and the protonated N-methylimidazole can enable the additive molecules to cooperate with water molecules to establish an uninterrupted rapid proton transport network in the electrolyte, so that protons are continuously transported from a bulk phase to an interface region, and the pH at the interface is kept stable.
4. The N-methylimidazole in the electrolyte can provide or accept protons for the deposition and dissolution process of manganese ions in the manganese anode, so that the kinetic process of deposition and dissolution is accelerated, and the capacity and the cycling stability of the manganese-based anode are obviously improved.
Drawings
FIG. 1 is a titration curve for example 1 using 0.5M aqueous sulfuric acid;
FIG. 2 is a symmetrical cell assembled using the electrolytes of comparative example 1 and example 4 at 1mA cm -2 Is 1mAh cm -2 Polarization voltage versus cycle time plot at deposition strip capacity;
FIG. 3 is a symmetrical cell assembled using the electrolytes of comparative example 1 and example 4 at 10mA cm -2 Is 10mAh cm -2 Polarization voltage versus cycle time plot at deposition strip capacity;
FIG. 4 is a zinc-copper half cell assembled from the electrolytes of comparative example 1 and example 4 at 1mA cm -2 Is 1mAh cm -2 Coulombic efficiency versus cycle number plot at deposition capacity of (c);
FIG. 5 is an XRD pattern of the surface of zinc foil after 50 cycles of electrolyte of comparative example 1 and example 4;
FIG. 6 is a scanning electron micrograph of the surface of a zinc foil after 50 cycles of the electrolyte of comparative example 1;
FIG. 7 is a scanning electron microscope image of the surface of a zinc foil after 50 cycles of the electrolyte of example 4;
FIG. 8 is a cyclic voltammogram of a full cell assembled using the electrolytes of comparative example 2 and example 6;
FIG. 9 is a graph of discharge capacity versus coulombic efficiency versus number of cycles for a full cell assembled using the electrolytes of comparative example 2 and example 6;
Detailed Description
In order that those skilled in the art will better understand the present application, a technical solution in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
Zinc foil preparation: cutting zinc foil with the thickness of 0.1mm into a circular sheet with the diameter of 12mm, and then cleaning and drying the circular sheet by ethanol ultrasonic.
Preparing copper foil: cutting copper foil into wafers with the diameter of 14mm, and then cleaning and drying the wafers by ethanol ultrasonic.
Preparing a glass fiber diaphragm: GF-D glass fibers were cut into 18mm discs for later use.
Preparing a positive electrode: synthesis of active substance polyaniline intercalated manganese dioxide 9mL of aniline monomer was dissolved in 450mL of CCl 4 In the method, 0.45g of potassium permanganate is dissolved in 450mL of deionized water, then the potassium permanganate and the potassium permanganate are mixed in a 1000mL round bottom flask, kept for 24 hours at 5 ℃, and centrifugally washed and freeze-dried to obtain polyaniline intercalated manganese dioxide. Adding a proper amount of N-methyl-pyrrolidone into a mixture of an anode active substance, ketjen black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1 to form slurry, coating the slurry on a stainless steel net with a diameter of 12mm, and drying to obtain an anode sheet, wherein the active substance loading is controlled to be 0.5-2.0mg cm -2 。
Example 1 (demonstration of buffer zone of N-methylimidazole in Zinc sulfate electrolyte)
A quantity of zinc sulfate heptahydrate was dissolved in deionized water to prepare a 2.0M zinc sulfate solution. 50mL of the solution was taken and 0.8mL of N-methylimidazole was added to prepare a suspension containing 0.2. 0.2M N-methylimidazole.
And (3) dropwise adding 0.5M sulfuric acid aqueous solution into the suspension under the magnetic stirring state by using an acid burette, recording the volume of the added sulfuric acid solution, and monitoring the pH corresponding to the system in real time by using a Lei Cidian sub-pH meter.
Comparative example 1 (electrolyte without multifunctional buffer additive)
Dissolving a certain amount of zinc sulfate heptahydrate and manganese sulfate monohydrate in deionized water to obtain a solution containing 2MZnSO 4 With 0.2M MnSO 4 Is ready for use of electrolyte
Example 2 (electrolyte contains 0.05M N-methylimidazole)
Mixing a certain amount of zinc sulfate heptahydrate, N-methylimidazole, 0.5M sulfuric acid aqueous solution and deionized water to obtain a solution containing 2M ZnSO 4 0.05M N-methylimidazole and electrolyte with ph=4.0 were ready for use.
Example 3 (electrolyte containing 0.1. 0.1M N-methylimidazole)
Mixing a certain amount of zinc sulfate heptahydrate, N-methylimidazole, 0.5M sulfuric acid aqueous solution and deionized water to obtain a solution containing 2M ZnSO 4 0.1M N-methylimidazole and electrolyte with ph=4.0 were ready for use.
Example 4 (electrolyte contains 0.2. 0.2M N-methylimidazole)
Mixing a certain amount of zinc sulfate heptahydrate, N-methylimidazole, 0.5M sulfuric acid aqueous solution and deionized water to obtain a solution containing 2M ZnSO 4 0.2M N-methylimidazole and electrolyte with ph=4.0 were ready for use.
Example 5 (electrolyte contains 0.5. 0.5M N-methylimidazole)
Mixing a certain amount of zinc sulfate heptahydrate, N-methylimidazole, 0.5M sulfuric acid aqueous solution and deionized water to obtain a solution containing 2M ZnSO 4 0.5M N-methylimidazole and electrolyte with ph=4.0 were ready for use.
Too high pH of the electrolyte can lead to the generation of basic zinc sulfate byproducts, while too low pH can aggravate hydrogen evolution reaction, so that the performance of the electrolyte can be exerted by maintaining a proper and stable pH value of the electrolyte-zinc anode interfaceThe important function is that of the device. As shown in FIG. 1, in 2.0M ZnSO 4 In the electrolyte, the buffer platform of the N-methylimidazole is 3.6-5.4. Basic zinc sulfate is stable at pH of 5.4, and the buffer platform of N-methylimidazole is close to the upper limit of basic zinc sulfate generation, which is very beneficial to realizing the buffer effect in a zinc sulfate system. The buffer effect is realized by the nitrogen atom in the 3 rd position and H on the N-methylimidazole molecule + Is used for reversible binding and release. For the solution of example 1, it can be seen from the titration curve that its corresponding pH buffer effective interval corresponds to 0.5. 0.5M H of 2-9mL 2 SO 4 Solutions showing a buffer additive utilization of over 70% when NMI is used as the buffer additive.
Symmetrical battery performance test: the CR2032 button cell was assembled in the order of the positive electrode case, zinc foil, separator, zinc foil, gasket, spring plate, and negative electrode case, and 120 μl of the electrolyte of the example or comparative example was injected between the two zinc foils. On a New Wipe battery test System, 1mA cm was followed -2 Is 1mAh cm -2 Is subjected to charge-discharge test. Fig. 2 is a polarization-time curve of comparative example 1 and example 4. It can be seen that the symmetrical cell using the electrolyte of comparative example 1 was short-circuited within 200 hours to fail the cell. In contrast, with the symmetrical cell of example 4, the cycle life reached 2600 hours, demonstrating that N-methylimidazole can significantly improve the cycle reversibility of the zinc anode. Furthermore, FIG. 3 shows that the temperature is 10mA cm -2 Is 10mAh cm -2 As a result of the charge and discharge test under the deposition stripping capacity condition, it can be seen that the cycle life of comparative example 1 was only 80 hours, whereas the cycle life of the symmetric battery employing example 4 reached 820 hours, and excellent performance was also exhibited under severe test conditions.
Table 1 shows the measurement at 1mA cm -2 Is 1mAh cm -2 The electrolyte solutions of examples 1-5 and the electrolyte solution of comparative example 1 were used for the symmetric cell test results. It can be seen that the addition of N-methylimidazole can significantly improve the cycle life of the zinc anode. However, with less N-methylimidazole, the electrostatic shield is used during depositionThe masking effect is not sufficiently remarkable and the ability to remove by-products is insufficient, and when the addition amount is large, the cell polarization is increased to adversely affect, so that the addition of 0.2M N-methylimidazole is considered as the most preferable implementation condition.
TABLE 1 symmetrical cell cycle charge and discharge times for examples 2-5, comparative example 1
Examples Cycle charge-discharge time
Comparative example 1 200h
Example 2 1400h
Example 3 2100h
Example 4 2600h
Example 5 2500h
Half cell performance test: the CR2032 button cell was assembled in the order of the positive electrode case, copper foil, separator, zinc foil, gasket, elastic sheet, and negative electrode case, and 120 μl of the electrolyte of example 4 or comparative example 1 was injected between the copper foil and the zinc foil. On a New Wipe battery test System, 1mA cm was followed -2 Is 1mAh cm -2 Is subjected to charge-discharge test. FIG. 4 shows the use of example 4And cycle number-coulombic efficiency plot of the half cell of comparative example 1. The half cell of comparative example 1 showed only 98.35% average coulombic efficiency in less than 50 cycles due to severe coulombic efficiency fluctuations due to dead zinc and by-product accumulation. While with the half cell of example 4, there was 99.28% average coulombic efficiency over 1500 stabilization cycles.
Surface by-product detection: symmetrical cells using the electrolytes of comparative example 1 and example 4 were prepared at 1mA cm -2 Is 1mAh cm -2 After 50 cycles of stripping capacity, the recycled zinc foil was rinsed clean with deionized water and tested using an X-ray diffraction (XRD) instrument. As can be seen from fig. 5, the zinc foil circulating in the electrolyte of comparative example 1 showed significant basic zinc sulfate diffraction peaks at the 8.1 °, 16.2 ° and 24.4 ° positions of the XRD pattern, demonstrating a substantial accumulation of byproducts. In contrast, the zinc foil circulating in the electrolyte of example 4 has no obvious basic zinc sulfate peak in XRD pattern, which proves that N-methylimidazole can obviously inhibit the accumulation of byproducts, thereby improving the reversibility of zinc cathode circulation.
And (3) cyclic morphology analysis: symmetrical cells using the electrolytes of comparative example 1 and example 4 were prepared at 1mA cm -2 Is 1mAh cm -2 After 50 cycles of the deposition stripping capacity, the zinc foil after the cycle is washed clean by deionized water, and the morphology analysis is carried out by using a scanning electron microscope. As can be seen from fig. 6, a large amount of irregular, loose sheet-like deposits were observed on the surface of the zinc foil circulated in the electrolyte of comparative example 1. These deposits can evolve as zinc dendrites during subsequent deposition, piercing the separator and causing the cell to short circuit. Whereas the surface of the zinc foil circulated in the electrolyte of example 4 in fig. 7 is very flat, this is because N-methylimidazole can limit the deposition of zinc ions in the 2D direction and reduce the nucleation size, thus flattening the deposited layer. On the other hand, the method can remove byproducts, keep the surface of the zinc foil fresh in the circulating process, ensure good combination of newly deposited zinc and a matrix, and further improve the reversibility of the zinc cathode.
Example 6 (electrolyte containing 0.2. 0.2M N-methylimidazole and 0.2M manganese ion)
Mixing a certain amount of zinc sulfate heptahydrate, manganese sulfate monohydrate, N-methylimidazole, 0.5M sulfuric acid aqueous solution and deionized water to obtain a solution containing 2M ZnSO 4 ，0.2M MnSO 4 0.2M N-methylimidazole and electrolyte with ph=4.0 were ready for use.
Control 2 (electrolyte containing 0.2M manganese ion)
Dissolving a certain amount of zinc sulfate heptahydrate, manganese sulfate monohydrate in deionized water to obtain a solution containing 2MZnSO 4 ，0.2M MnSO 4 Is ready for use.
Full cell test: the CR2032 button cell was assembled in the order of positive electrode case, positive electrode, separator, zinc foil, gasket, elastic sheet, negative electrode case, and 120 μl of the electrolyte of example 6 or comparative example 2 was injected between the positive electrode and the zinc foil. Full cells were first subjected to Cyclic Voltammetry (CV) using the CHI660E electrochemical workstation from the Shanghai Chenhua. The full cell using the electrolyte of example 6, both the cathodic peak and the anodic peak, were approximately 2 times the area of the full cell using the electrolyte of comparative example 2, indicating a significant increase in discharge capacity. For manganese oxide cathode materials, in addition to intercalation and deintercalation of zinc ions and protons, there is also a redox deposition dissolution behavior of manganese oxide, i.e. a conversion between Mn (ii) and Mn (IV). According to Nernst equation, mnO 2 Dissolution by discharge and Mn 2+ Exhibits a correlation with the proton concentration of the system. As can be seen from the CV curves in fig. 8, the addition of N-methylimidazole shifted the two cathode peaks positively (1.24V to 1.28V and 1.37V to 1.38V), and the anode peak at 1.57V shifted negatively to 1.55V, indicating that the full cell using the electrolyte of example 4 had a higher discharge voltage and less polarization. 1A g Using New Wei charge-discharge instrument -1 As can be seen from FIG. 9, the addition of N-methylimidazole resulted in an average discharge capacity of the full cell of 119.9mAh g -1 Lifting to 234.7mAh g -1 Almost doubles, and proves that the additive can obviously improve the capacity of the positive electrode by accelerating the deposition and dissolution process of the manganese oxide.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. An electrolyte additive for a water-based zinc ion battery is characterized in that the electrolyte additive is imidazole and imidazole derivatives with alkyl, carboxyl, amino, nitro and halogen on side chains.
2. An electrolyte additive for an aqueous zinc-ion battery according to claim 1, wherein the electrolyte additive is N-methylimidazole or other imidazole derivatives, and the concentration of the additive in the electrolyte is 0.05-0.5M.
3. An electrolyte additive for an aqueous zinc-ion battery according to claim 1, characterized in that the electrolyte additive has a pKa value between 3 and 8, comprising imidazole, 2-methylimidazole, 4-methylimidazole, histamine, benzimidazole, 1-methyl-1H-imidazole-4, 5-dicarboxylic acid, 2-nitroimidazole, 4-bromo-1H-imidazole, N-butylimidazole.
4. An aqueous zinc-ion battery electrolyte comprising deionized water, a zinc salt electrolyte, and the electrolyte additive of claim 1.
5. The aqueous zinc-ion battery electrolyte according to claim 4, wherein the pH of the electrolyte is 3.5-5.4.
6. The aqueous zinc-ion battery electrolyte according to claim 5, wherein the electrolyte is one or a combination of two or more of zinc sulfate, zinc nitrate, zinc trifluoromethane sulfonate and zinc chloride.
7. The aqueous zinc-ion battery electrolyte of claim 6, wherein the zinc salt electrolyte concentration is 1-3M.
8. An aqueous zinc-ion battery, characterized in that the electrolyte is an electrolyte according to one of claims 4 to 7.
CN202310967837.2A 2023-08-03 2023-08-03 Electrolyte additive for aqueous zinc ion secondary battery and battery thereof Pending CN116826193A (en)

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Application Number Priority Date Filing Date Title
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