Nicotinamide-containing aqueous zinc-ion battery electrolyte, battery, and preparation method

Abstract

The application belongs to the technical field of battery electrolyte, and particularly relates to a water-based zinc ion battery electrolyte containing nicotinamide, a battery and a preparation method. The water-based zinc ion battery electrolyte provided by the application comprises a solvent, a zinc salt, nicotinamide and 3-(1,2,4-triazol-1-yl) methyl benzoate. Nicotinamide is enriched in the anode / electrolyte interface through chemical adsorption, which not only blocks the deposition of by-products and inhibits dendrites, but also significantly reduces the zinc nucleation overpotential, increases the uniform nucleation site, induces three-dimensional diffusion growth, realizes (002) crystal plane dominated dense zinc deposition, and thus significantly reduces the polarization voltage. 3-(1,2,4-triazol-1-yl) methyl benzoate preferentially reacts with water, passivates the reactivity of water, and further inhibits the side reaction in the water-based electrolyte. Thanks to the above-mentioned synergistic mechanism, the electrolyte endows the water-based zinc ion battery with high specific capacity and excellent cycle stability.

Description

Technical Field

[0001] This invention belongs to the field of battery technology, specifically relating to an aqueous zinc-ion battery electrolyte containing nicotinamide that can suppress dendrites and byproducts, a method for preparing the electrolyte, and an aqueous zinc-ion battery made from the electrolyte. Background Technology

[0002] As the world's reliance on renewable energy deepens, developing efficient and sustainable energy storage technologies has become a key task in the energy sector. Among numerous energy storage technologies, aqueous zinc-ion batteries (ZIBs) stand out due to their superior performance, demonstrating enormous application potential. Their high energy density (up to 820 mAh / g) provides strong support for energy storage, while their low cost and inherent safety give them a unique advantage in market competition.

[0003] However, despite the numerous advantages of aqueous zinc-ion batteries, they still face many challenges in practical applications. Among these, the corrosion of metallic zinc and dendrite growth are particularly prominent. During battery charging and discharging, the local pH value of the electrolyte undergoes significant changes, creating an alkaline environment. This environment accelerates the corrosion of the zinc anode, severely impacting battery lifespan and performance stability. Furthermore, the reaction between free water molecules and zinc triggers a "tip effect," which further exacerbates zinc dendrite growth. The disordered growth of zinc dendrites not only leads to internal short circuits but also poses a series of safety hazards, significantly limiting the large-scale commercial application of aqueous zinc-ion batteries.

[0004] Recent studies have shown that achieving compact and horizontally aligned Zn deposition with a (002) crystal texture is crucial for addressing these issues and improving the reversibility and lifespan of Zn metal anodes. In the crystal structure of zinc, the (002) crystal plane exhibits excellent corrosion resistance and dendrite growth suppression due to its lower surface energy and stronger interatomic interactions. Studies have shown that zinc deposits with (002) crystal plane orientation are flatter, with an inclination angle to the substrate of only 0–30°, much smaller than the 70–90° of the (100) and (101) crystal planes. This structural advantage results in higher reversibility and stability in zinc anodes. Therefore, achieving preferential growth of the (002) crystal plane is key to improving zinc anode performance. Based on the regulatory role of the electrolyte, developing environmentally friendly and efficient electrolyte additives to optimize zinc deposition behavior has become a key strategy for promoting the development of green and safe aqueous zinc-ion batteries. Summary of the Invention

[0005] One objective of this invention is to provide an aqueous zinc-ion battery electrolyte containing nicotinamide. By adding nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate to the electrolyte, the electrode / electrolyte interface is adjusted, thereby significantly suppressing dendrites and byproducts and improving battery performance.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: an aqueous zinc-ion battery electrolyte containing nicotinamide, comprising a solvent, a zinc salt, and an additive, wherein the additive is nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate, the concentration of the additive in the solvent is 3-25 wt%, and the concentration of the zinc salt in the solvent is 1.5-4 mol / kg.

[0007] Further improvements to aqueous zinc-ion battery electrolytes containing nicotinamide:

[0008] Preferably, the mass ratio of nicotinamide to methyl 3-(1,2,4-triazol-1-yl)benzoate is 1:8 to 8:1.

[0009] Preferably, the solvent is deionized water.

[0010] Preferably, the zinc salt is zinc sulfate or zinc trifluoromethanesulfonate.

[0011] The second objective of this invention is to provide a method for preparing the above-mentioned aqueous zinc-ion battery electrolyte containing nicotinamide, comprising the following steps: dissolving nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate in a solvent to obtain a mixed solution of nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate, then adding zinc salt and stirring evenly to obtain the aqueous zinc-ion battery electrolyte containing nicotinamide.

[0012] The third objective of this invention is to provide an aqueous zinc-ion battery prepared from the above-mentioned aqueous zinc-ion battery electrolyte containing nicotinamide.

[0013] As a further improvement to aqueous zinc-ion batteries:

[0014] Preferably, the aqueous zinc-ion battery is assembled by sequentially stacking a positive electrode, a separator, a negative electrode, a gasket, and a spring, and then injecting an aqueous zinc-ion battery electrolyte containing nicotinamide.

[0015] Preferably, the positive electrode is ammonium vanadate or copper sheet.

[0016] Preferably, the diaphragm is a non-woven fabric or filter paper.

[0017] Preferably, the negative electrode is a zinc sheet.

[0018] The advantages of this invention compared to the prior art are as follows:

[0019] (1) This invention provides an aqueous zinc-ion battery electrolyte containing nicotinamide. It innovatively introduces nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate as co-additives into the zinc salt electrolyte to obtain an electrolyte solution with good conductivity. This allows for the regulation of zinc deposition kinetics during the charge-discharge process of the aqueous zinc-ion battery and the suppression of water activity, thereby improving the reversibility of the zinc anode. Nicotinamide is enriched at the anode / electrolyte interface through chemical adsorption, which not only prevents byproduct deposition and inhibits dendrite formation but also significantly reduces the zinc nucleation overpotential, increases uniform nucleation sites, and induces three-dimensional diffusion growth, achieving dense zinc deposition dominated by the (002) crystal plane, thus significantly reducing the polarization voltage. Methyl 3-(1,2,4-triazol-1-yl)benzoate preferentially reacts with water, passivating the reactivity of water and further suppressing side reactions in the aqueous electrolyte. Thanks to the above synergistic mechanism, this electrolyte endows the aqueous zinc-ion battery with high specific capacity and excellent cycle stability.

[0020] (2) This invention introduces trace amounts of inexpensive additives into a low-concentration salt solution, enabling the one-step construction of a novel aqueous zinc-ion battery electrolyte containing nicotinamide, without any complex pretreatment. This electrolyte allows for precise control of Zn content. 2+ Preferred deposition on the (002) crystal plane significantly suppresses hydrogen evolution side reactions, enabling the battery to achieve both high rate capability and high capacity cycle stability. A high-performance aqueous zinc-ion battery can be obtained by simply assembling the electrolyte with the positive electrode, zinc negative electrode, gasket, and spring. Compared to existing systems, this technology exhibits a lower zinc nucleation barrier, higher discharge specific capacity, and slower positive electrode capacity decay, outstanding cycle reversibility, simple process, and low cost. Attached Figure Description

[0021] Figure 1 10 mA / cm 2 XRD comparison images of zinc sheets deposited for 1 hour in different electrolytes prepared in Example 3 and Comparative Examples 1, 2 and 3 at different current densities.

[0022] Figure 2 To assemble Zn / / Zn symmetric cells using the electrolytes of Example 3 and Comparative Examples 1, 2, and 3, at 10 mA·cm⁻¹ -2 -10 mAh·cm -2 Comparison of cyclic performance under test conditions.

[0023] Figure 3 To assemble Zn / / Cu batteries using the electrolytes of Example 3 and Comparative Examples 1, 2, and 3, at 0.5 mA·cm -2 -0.5 mAh·cm-2 Coulomb efficiency under test conditions.

[0024] Figure 4 To assemble Zn / / NH4V4O using the electrolytes of Example 3 and Comparative Examples 1, 2, and 3 10 Full battery, at 5 A·g -1 Comparison of cycling performance at current density. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0026] Example 1

[0027] This embodiment provides an aqueous zinc-ion battery electrolyte containing nicotinamide, the preparation method of which includes the following steps:

[0028] S1. Dissolve 1.5 g of nicotinamide and 1.5 g of methyl 3-(1,2,4-triazol-1-yl)benzoate in 100 g of deionized water by ultrasonication to obtain a mixed solution; the total concentration of the two additives in the deionized water is 3 wt%.

[0029] S2. Add 0.15 mol of zinc trifluoromethanesulfonate (concentration of 1.5 mol / kg in deionized water) to the above mixed solution, stir evenly, and obtain an aqueous zinc-ion battery electrolyte 1 that can suppress dendrites and by-products.

[0030] Example 2

[0031] This embodiment provides an aqueous zinc-ion battery electrolyte containing nicotinamide, the preparation method of which includes the following steps:

[0032] S1. 12.5 g of nicotinamide and 12.5 g of methyl 3-(1,2,4-triazol-1-yl)benzoate were dissolved in 100 g of deionized water by ultrasonication to obtain a mixed solution; the total concentration of the two additives in the deionized water was 25 wt%.

[0033] S2. Add 0.2 mol of zinc sulfate (2 mol / kg in deionized water) to the above mixed solution and stir until homogeneous to obtain an aqueous zinc-ion battery electrolyte 2 that can suppress dendrites and by-products.

[0034] Example 3

[0035] This embodiment provides an aqueous zinc-ion battery electrolyte containing nicotinamide, the preparation method of which includes the following steps:

[0036] S1. Dissolve 8 g of nicotinamide and 1 g of methyl 3-(1,2,4-triazol-1-yl)benzoate in 100 g of deionized water by ultrasonication to obtain a mixed solution; the total concentration of the two additives in the deionized water is 9 wt%.

[0037] S2. Add 0.35 mol of zinc trifluoromethanesulfonate (concentration of 3.5 mol / kg in deionized water) to the above mixed solution, stir evenly, and obtain an aqueous zinc-ion battery electrolyte 3 that can suppress dendrites and by-products.

[0038] Example 4

[0039] This embodiment provides an aqueous zinc-ion battery electrolyte containing nicotinamide, the preparation method of which includes the following steps:

[0040] S1. Dissolve 1 g of nicotinamide and 8 g of methyl 3-(1,2,4-triazol-1-yl)benzoate in 100 g of deionized water by ultrasonication to obtain a mixed solution; the total concentration of the two additives in the deionized water is 9 wt%.

[0041] S2. Add 0.4 mol of zinc sulfate (concentration of 4 mol / kg in deionized water) to the above mixed solution, stir evenly, and obtain an aqueous zinc-ion battery electrolyte 4 that can suppress dendrites and by-products.

[0042] Comparative Example 1

[0043] This comparative example provides an aqueous zinc-ion battery electrolyte, the preparation method of which includes the following steps:

[0044] S1. Add 9 g of nicotinamide to 100 g of deionized water and dissolve by ultrasonication to obtain a nicotinamide solution with a concentration of 9 wt%.

[0045] S2. Add 0.35 mol of zinc trifluoromethanesulfonate (concentration of 3.5 mol / kg in deionized water) to the above nicotinamide solution, stir well, and prepare ordinary aqueous zinc-ion battery electrolyte 1.

[0046] Comparative Example 2

[0047] This comparative example provides an aqueous zinc-ion battery electrolyte, the preparation method of which includes the following steps:

[0048] S1. Add 9 g of methyl 3-(1,2,4-triazol-1-yl)benzoate to 100 g of deionized water and dissolve by ultrasonication to obtain a methyl 3-(1,2,4-triazol-1-yl)benzoate solution with a concentration of 9 wt%.

[0049] S2. Add 0.35 mol of zinc trifluoromethanesulfonate (concentration of 3.5 mol / kg in deionized water) to the above methyl 3-(1,2,4-triazol-1-yl)benzoate solution, stir well, and prepare ordinary aqueous zinc-ion battery electrolyte 2.

[0050] Comparative Example 3

[0051] This comparative example provides a pure zinc trifluoromethanesulfonate electrolyte, the preparation method of which includes the following steps:

[0052] Add 0.35 mol of zinc trifluoromethanesulfonate to 100 g of deionized water at a concentration of 3.5 mol / kg, stir well, and obtain an additive-free ordinary aqueous zinc-ion battery electrolyte 3.

[0053] Figure 1 The XRD pattern is shown. Zinc sheets were deposited in different electrolytes prepared in Example 3 and Comparative Examples 1, 2, and 3. Both the positive and negative electrodes were zinc sheets. The specific test steps are as follows: 10 mA / cm 2 XRD analysis was performed on the positive zinc electrode after one hour of discharge at a given current density; from Figure 1 As can be seen, compared with the pure zinc trifluoromethanesulfonate electrolyte (3.5 mol / kg, no additives) of Comparative Example 3, the electrolyte of Comparative Example 1 with only nicotinamide added, and the electrolyte of Comparative Example 2 with only methyl 3-(1,2,4-triazol-1-yl)benzoate added, the electrolyte of Example 3 containing a mixed additive system of nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate showed more obvious (002) crystal plane orientation growth, indicating that the addition of nicotinamide can induce (002) crystal plane texture growth and inhibit zinc dendrite growth.

[0054] Figure 2 The cycle stability of Zn / / Zn batteries was compared. Different electrolytes prepared in Example 3 and Comparative Examples 1, 2, and 3 were assembled into zinc-zinc batteries using a positive electrode (zinc sheet), a separator (glass fiber), a negative electrode (zinc sheet), a gasket, and a spring. The specific test procedures are as follows: 10 mA·cm⁻¹ was applied... -2 A current was applied to the symmetrical cell, and the polarization voltage was recorded as a function of time at 10 mA·cm⁻¹. -2 -10 mAh·cm -2Under the test conditions, compared with the pure zinc trifluoromethanesulfonate electrolyte of Comparative Example 3, the electrolyte of Comparative Example 1 with only nicotinamide added, and the electrolyte of Comparative Example 2 with only methyl 3-(1,2,4-triazol-1-yl)benzoate added, the electrolyte cycle stability of the mixed additive system containing nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate in Example 3 was significantly improved.

[0055] Figure 3 The coulombic efficiency of Zn / / Cu half-cells assembled with different electrolytes prepared in Example 3 and Comparative Examples 1, 2, and 3 was compared. Aqueous zinc-ion battery electrolytes were assembled with a positive electrode (copper sheet), a separator (filter paper), a negative electrode (zinc sheet), a gasket, and a spring to form a zinc-copper half-cell. A 0.5 mA·cm⁻¹ pressure was applied to the Zn / / Cu cell. -2 The charging and discharging current was set, the discharge time was 60 minutes, and the charging cutoff voltage was 0.5 V. The coulombic efficiency was recorded as a function of the number of cycles. Figure 3 It can be seen that the Zn / / Cu half-cell containing nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate additives in Example 3 has an average coulombic efficiency of 99.63%, which is significantly higher than that of the pure zinc trifluoromethanesulfonate electrolyte in Comparative Example 3, the electrolyte in Comparative Example 1 with only nicotinamide added, and the electrolyte in Comparative Example 2 with only methyl 3-(1,2,4-triazol-1-yl)benzoate added.

[0056] Figure 4 The cycle stability of full cells assembled with different electrolytes prepared in Example 3 and Comparative Examples 1, 2, and 3 was compared. The positive electrode was ammonium vanadate, and the negative electrode was a zinc sheet. The specific test steps are as follows: the current density was 5 A·g. -1 Record the trend of the specific capacity of the Zn / / NVO full cell with the number of cycle cycles. For example... Figure 4 As shown, using the electrolyte from Example 3 containing nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate, the initial specific capacity reached as high as 330.93 mAh·g. -1 After 1000 cycles, it still has a retention rate of nearly 100%, indicating that the specific capacity of the positive electrode decays slowly and the cycle stability is significantly higher than that of the pure zinc trifluoromethanesulfonate electrolyte in Comparative Example 3, the electrolyte with only nicotinamide added in Comparative Example 1, and the electrolyte with only methyl 3-(1,2,4-triazol-1-yl)benzoate added in Comparative Example 2.

[0057] Different electrolytes prepared in Examples 1, 2, and 4 were assembled with a positive electrode (zinc sheet), a separator (glass fiber), a negative electrode (zinc sheet), a gasket, and a spring to form a Zn / / Zn battery. At 10 mA·cm⁻¹ -2 -10 mAh·cm -2Under the test conditions, the Zn / / Zn battery was able to cycle stably for 350 hours, 330 hours and 360 hours respectively, which were all superior to the pure zinc trifluoromethanesulfonate electrolyte of Comparative Example 3, the electrolyte of Comparative Example 1 with only nicotinamide added, and the electrolyte of Comparative Example 2 with only methyl 3-(1,2,4-triazol-1-yl)benzoate added, thus confirming the effectiveness of the synergistic effect of the two additives in the electrolytes of Examples 1, 2 and 4.

[0058] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. An aqueous zinc-ion battery electrolyte containing nicotinamide, characterized in that, The components include a solvent, a zinc salt, and additives, wherein the additives are nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate, the concentration of the additives in the solvent is 3-25 wt%, and the concentration of the zinc salt in the solvent is 1.5-4 mol / kg.

2. The aqueous zinc-ion battery electrolyte containing nicotinamide according to claim 1, characterized in that, The mass ratio of nicotinamide to methyl 3-(1,2,4-triazol-1-yl)benzoate is 1:8 to 8:

1.

3. The aqueous zinc-ion battery electrolyte containing nicotinamide according to claim 1, characterized in that, The solvent is deionized water.

4. The aqueous zinc-ion battery electrolyte containing nicotinamide according to claim 1, characterized in that, The zinc salt is zinc sulfate or zinc trifluoromethanesulfonate.

5. A method for preparing the nicotinamide-containing aqueous zinc-ion battery electrolyte according to any one of claims 1-4, characterized in that, The process includes the following steps: nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate are dissolved in a solvent to obtain a mixed solution of nicotinamide and methyl 3-(1,2,4-triazol-1-yl)benzoate; zinc salt is then added and stirred until homogeneous to obtain an aqueous zinc-ion battery electrolyte containing nicotinamide.

6. An aqueous zinc-ion battery prepared with the nicotinamide-containing aqueous zinc-ion battery electrolyte according to any one of claims 1-4.

7. The aqueous zinc-ion battery according to claim 6, characterized in that, The aqueous zinc-ion battery is assembled by sequentially stacking a positive electrode, a separator, a negative electrode, a gasket, and a spring, and then injecting an aqueous zinc-ion battery electrolyte containing nicotinamide.

8. The aqueous zinc-ion battery according to claim 7, characterized in that, The positive electrode is ammonium vanadate or copper sheet.

9. The aqueous zinc-ion battery according to claim 7, characterized in that, The diaphragm is made of non-woven fabric or filter paper.

10. The aqueous zinc-ion battery according to claim 7, characterized in that, The negative electrode is a zinc sheet.

Images