A water-based zinc ion battery electrolyte based on arbutin and a preparation method thereof

Abstract

The application relates to the technical field of zinc ion batteries, and discloses a zinc ion battery electrolyte based on arbutin and a preparation method thereof. The zinc ion battery electrolyte comprises the following components: a zinc salt, arbutin and a solvent. Multiple hydroxyl groups in the molecule of the key component arbutin can act as hydrogen bond donors to form a hydrogen bond network with water molecules or solvents in the electrolyte, which helps to reconstruct the electrolyte interface structure and inhibit the hydrogen evolution side reaction. In addition, the large molecular volume and the multi-hydroxyl structure of arbutin can provide steric hindrance by using the steric hindrance effect, delay the rapid reduction of zinc ions on the electrode surface, and thus inhibit the dendrite growth. Moreover, the polar groups of the sugar molecule can be adsorbed on the zinc negative electrode surface, homogenize the interface electric field, and promote the uniformity of zinc deposition. Through the synergistic effect of multiple mechanisms, the cycle stability of the battery is improved, and the service life of the battery is prolonged.

Description

Technical Field

[0001] This invention relates to the field of zinc-ion battery technology, and more specifically, to a method for preparing an aqueous zinc-ion battery electrolyte based on arbutin and the electrolyte itself. Background Technology

[0002] With the rapid development of the large-scale energy storage industry, safe, low-cost, and environmentally friendly energy storage battery technology has become a key research focus in the new energy field. Aqueous zinc-ion batteries (AZIBs) overcome the drawbacks of traditional organic electrolytes, such as flammability, explosiveness, high cost, and severe environmental pollution. They are widely recognized as a highly promising candidate energy storage system for large-scale energy storage scenarios due to their numerous core advantages, including low manufacturing costs, high intrinsic safety, good environmental compatibility, and excellent ionic conductivity. Meanwhile, zinc metal anodes possess advantages such as high theoretical specific capacity, low redox potential, abundant crustal resources, and mature manufacturing processes, making them the preferred core anode material for aqueous zinc-ion batteries and providing a solid foundation for high-performance and low-cost battery applications.

[0003] Despite the numerous advantages of aqueous zinc-ion batteries, several technical defects remain to be addressed in the zinc metal anode during repeated charge-discharge cycles in the typical operating environment of weakly acidic or neutral aqueous electrolytes. These defects primarily stem from three major issues: dendrite growth, hydrogen evolution side reactions, and electrode corrosion. These issues severely hinder the industrialization and large-scale application of aqueous zinc-ion batteries. Specifically, the disordered growth of zinc dendrites can easily puncture the battery separator, causing internal short circuits, a sharp drop in capacity, and significantly reducing battery safety. The hydrogen evolution reaction triggered by water molecules in the electrolyte continuously consumes battery charge, reducing coulombic efficiency, and the generated gas can easily lead to battery bulging and failure. Long-term electrode corrosion continuously consumes the active material of the zinc anode, damaging the stability of the electrode interface structure and ultimately significantly shortening the overall cycle life of the battery, becoming a key bottleneck limiting the performance improvement of aqueous zinc-ion batteries.

[0004] To address various interfacial issues in zinc anodes, electrolyte additive modification technology has become a mainstream approach for stabilizing zinc anodes and optimizing battery performance due to its ease of operation, significant modification effects, and strong adaptability. Compared to traditional synthetic additives, natural extract additives offer unique advantages such as excellent biocompatibility, complete degradability, environmental friendliness, and abundant functional groups. These advantages avoid the drawbacks of traditional chemical additives, including high toxicity, significant bioaccumulation risk, and environmental unfriendliness. Aligning with the development trend of green energy technologies, natural extracts demonstrate enormous application potential in the modification of aqueous zinc-ion battery anodes. Natural extract molecules generally contain active functional groups such as hydroxyl and carboxyl groups. Through multiple mechanisms, including interfacial adsorption, electrolyte solvation structure reconstruction, hydrogen bond network regulation, and the construction of zinc-loving active sites, they can simultaneously inhibit zinc dendrite growth, hydrogen evolution side reactions, and electrode corrosion, effectively optimizing zinc ion deposition behavior and significantly improving battery cycle stability and coulombic efficiency.

[0005] Currently, research on natural extract additives has made phased progress, and various natural functional molecules have been proven to effectively improve the electrochemical performance of zinc anodes. For example, gum arabic can reconstruct the electrolyte hydrogen bond network through its own polar functional groups, reducing the electrochemical activity of free water molecules, and achieving an ultra-long stable cycle of 2700 hours at an addition of 1.0%; adenosine can optimize the zinc ion solvation structure through a multi-point synergistic regulation mechanism, inducing zinc ions to be deposited in a directional and orderly manner along the (002) crystal plane, thereby increasing the battery cycle life to 2650 hours. Furthermore, the team led by Zhou Liangjun and Wei Weifeng at Central South University innovatively used amikacin sulfate (AS), an aminoglycoside, as an electrolyte additive. This molecule is rich in zinc-loving active groups and can reconstruct the hydrogen bond network and solvation structure of the electrolyte through interactions with water molecules and zinc ions. At the same time, it can stably adsorb on the surface of the zinc anode to block side reactions. During cycling, it can decompose in situ to form a dense protective interface layer, precisely controlling the zinc ion deposition behavior. Ultimately, this achieves long-term stable cycling at ultra-high rates and high charge-discharge depths, further verifying the technical feasibility of natural functional molecules in the field of zinc anode modification.

[0006] However, current electrolyte additive technologies still have significant shortcomings, making it difficult to meet the application requirements of large-scale, long-lasting, and highly safe aqueous zinc-ion batteries. On the one hand, traditional synthetic small-molecule additives are mostly toxic systems such as organometallic compounds, which have problems such as high biotoxicity, easy accumulation in organisms, and difficulty in environmental degradation. They can easily cause environmental pollution after battery disposal, resulting in poor application safety and environmental friendliness. At the same time, most traditional additives have single functions, only addressing single problems such as dendrite growth, hydrogen evolution reaction, and electrode corrosion. They cannot simultaneously adapt to the multi-dimensional failure mechanisms of zinc anodes, requiring the use of multiple additives in combination, which greatly increases the complexity of electrolyte formulation and production costs, hindering industrial promotion. On the other hand, existing natural extract additives still have obvious performance defects. The stability of different natural extract components varies greatly, which can easily lead to batch-to-batch performance fluctuations in batteries. Moreover, during long-term battery cycling, natural molecules are prone to degradation and consumption failure, causing the electrode interface protection function to weaken, resulting in technical bottlenecks such as insufficient durability and poor long-term cycle stability.

[0007] To address the numerous shortcomings of existing technologies, developing a novel natural electrolyte additive that is non-toxic, biodegradable, multifunctional, highly stable, low-cost, and suitable for long-term cycling has become a core research direction for overcoming the bottlenecks in the application of aqueous zinc-ion batteries. The arbutin used in this invention is a naturally extracted active ingredient from the leaves of the bearberry plant (Arbutinus argentea), possessing non-toxic, harmless, and completely biodegradable characteristics, making it friendly to humans and the environment, perfectly aligning with the development concept of green and sustainable energy technologies. Simultaneously, the arbutin molecule possesses multiple active functional groups such as phenolic hydroxyl groups and glucose residues, overcoming the limitations of traditional additives with single functions. It can achieve comprehensive modification of the zinc anode interface through multi-mechanism synergistic action: it can stably adsorb onto the zinc anode surface to construct a dense protective film, isolating the electrolyte from direct contact with the electrode to inhibit corrosion and hydrogen evolution reactions; it can also reconstruct the electrolyte solvation structure and hydrogen bond network, reducing water molecule activity, precisely controlling the uniform deposition of zinc ions, and fundamentally inhibiting zinc dendrite growth. Furthermore, arbutin can be extracted on a large scale from agricultural by-products and natural plant resources, with a wide range of raw material sources and controllable preparation costs, making it a promising candidate for industrial application. It can effectively solve many pain points in existing technologies, such as poor safety, limited functionality, insufficient stability, lack of durability, and complex processes, providing a new technical path for the industrial application of high-performance, long-life, and green aqueous zinc-ion batteries. Summary of the Invention

[0008] In view of this, the present invention proposes an aqueous zinc-ion battery electrolyte based on arbutin and its preparation method, aiming to solve the problems of high toxicity, poor biocompatibility and single function of traditional additives in the current technology, poor stability of existing natural additive components, easy degradation and failure after long-term cycling, insufficient durability, prominent problems of zinc anode dendrite growth, hydrogen evolution side reaction and electrode corrosion, poor battery cycle stability, short service life and limited industrial application.

[0009] This invention proposes an aqueous zinc-ion battery electrolyte based on arbutin, wherein the zinc-ion battery electrolyte comprises the following components: Zinc salt, arbutin, solvent.

[0010] Preferably, the zinc salt includes one or more of ZnSO4, ZnCl2 and Zn(OTf)2; The solvent is water.

[0011] Preferably, the mass concentration of arbutin in the zinc-ion battery electrolyte is 0.1% to 1%.

[0012] Preferably, the concentration of zinc salt in the zinc-ion battery electrolyte is 0.1~4 mol / L.

[0013] This invention provides a method for preparing an aqueous zinc-ion battery electrolyte based on arbutin, comprising the following steps: The arbutin-based aqueous zinc-ion battery electrolyte is obtained by mixing zinc salt, arbutin and solvent and then sonicating.

[0014] Preferably, the temperature of the ultrasound is 20~30℃ and the duration is 5~15min.

[0015] This invention provides an application of an arbutin-based aqueous zinc-ion battery electrolyte in zinc-ion batteries.

[0016] Preferably, the zinc-ion battery includes a positive electrode, a negative electrode, and an arbutin-based aqueous zinc-ion battery electrolyte.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides an aqueous zinc-ion battery electrolyte based on arbutin. On one hand, the multiple hydroxyl groups in the arbutin molecule can act as hydrogen bond donors, forming a hydrogen bond network with water molecules or solvent in the electrolyte, which helps to reconstruct the electrolyte interface structure and suppress hydrogen evolution side reactions. On the other hand, its large molecular volume and multi-hydroxyl structure can provide steric hindrance through steric hindrance, delaying the rapid reduction of zinc ions on the electrode surface and thus inhibiting dendrite growth. Furthermore, the polar groups of the sugar molecules can adsorb onto the zinc anode surface, homogenizing the interfacial electric field and promoting the uniformity of zinc deposition. Through the synergistic effect of multiple mechanisms, the battery cycle stability is improved, and the battery life is extended. Attached Figure Description

[0018] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings: Figure 1 A Zn||Zn symmetric cell prepared using the electrolyte of Comparative Example 1 was tested at 1 mA·cm⁻¹. -2 Current density and 1 mA·h·cm -2 Cyclic charge-discharge curves at deposition capacity; Figure 2 A Zn||Zn symmetric cell prepared using the electrolyte of Example 1 was tested at 1 mA·cm⁻¹. -2 Current density and 1 mA·h·cm -2 Cyclic charge-discharge curves at deposition capacity.

[0019] Figure 3 A Zn||Zn symmetric cell prepared using the electrolyte of Example 1 was tested at 10 mA·cm⁻¹. -2 Current density and 1 mA·h·cm -2 Cyclic charge-discharge curves at deposition capacity.

[0020] Figure 4 A Zn||Zn symmetric cell prepared using the electrolyte of Example 1 was tested at 5 mA·cm⁻¹. -2 Current density and 1 mA·h·cm -2 Cyclic charge-discharge curves at deposition capacity.

[0021] Figure 5 The hydrogen evolution potential of zinc-ion batteries assembled using the electrolytes prepared in Example 1 and Comparative Example 1 is measured using linear sweep voltammetry (LSV) in zinc / / titanium batteries. Figure 6 The test results are obtained by chronoamperometry testing of zinc-ion batteries assembled with the electrolytes prepared in Example 1 and Comparative Example 1. Detailed Implementation

[0022] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0023] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0024] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0025] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0026] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0027] This invention proposes an aqueous zinc-ion battery electrolyte based on arbutin, wherein the zinc-ion battery electrolyte comprises the following components: Zinc salt, arbutin, solvent.

[0028] The arbutin has a molecular weight of 272.251 and a molecular formula of C2. 20 H 27 NO 11 The structural formula is as follows: In this invention, the zinc salt includes one or more of ZnSO4, ZnCl2 and Zn(OTf)2; The solvent is water.

[0029] In this invention, the mass concentration of arbutin in the zinc-ion battery electrolyte is 0.1% to 1%, preferably 0.15% to 0.7%, more preferably 0.18% to 0.4%, and even more preferably 0.2% to 0.3%.

[0030] In this invention, the concentration of zinc salt in the zinc-ion battery electrolyte is 0.1~4 mol / L, preferably 0.5~3 mol / L, more preferably 1.0~2.5 mol / L, and even more preferably 2.0 mol / L.

[0031] This invention provides a method for preparing an aqueous zinc-ion battery electrolyte based on arbutin, comprising the following steps: The arbutin-based aqueous zinc-ion battery electrolyte is obtained by mixing zinc salt, arbutin and solvent and then sonicating.

[0032] In this invention, the temperature of the ultrasound is 20~30℃, and can be selected from 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, 28℃, 29℃, and 30℃; the time is 5~15min, and can be selected from 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, and 15min.

[0033] This invention provides an application of an arbutin-based aqueous zinc-ion battery electrolyte in zinc-ion batteries.

[0034] In this invention, the zinc-ion battery includes a positive electrode, a negative electrode, and an arbutin-based aqueous zinc-ion battery electrolyte.

[0035] Example 1 Weigh 5.7512g ZnSO4·7H2O into a sample bottle, add deionized water and stir to dissolve. Transfer the solution to a volumetric flask and make up to 10mL. After it is completely dissolved, pour it into the sample bottle.

[0036] Add 0.02 g of arbutin to the sample vial, transfer it to an ultrasonic cleaner, and sonicate at 25 °C for 5 min to obtain an electrolyte with a zinc sulfate concentration of 2 mol / L and an arbutin concentration of 0.2 wt%.

[0037] Comparative Example 1 Weigh 5.7512g ZnSO4·7H2O into a sample bottle, add deionized water and stir to dissolve. Transfer to a volumetric flask and make up to 10mL. After complete dissolution, pour into the sample bottle and transfer to an ultrasonic cleaner. Sonicate at 25℃ for 5min to obtain an electrolyte with a zinc sulfate concentration of 2mol / L.

[0038] The performance of the electrolytes prepared in Examples 1-3 and Comparative Example 1 was tested using the following methods: The assembled Zn||Zn symmetric battery, with zinc foil as the positive and negative electrodes, glass fiber membrane as the separator, and electrolyte prepared in Example 1 or Comparative Example 1, was assembled into a C2032 button cell in an air atmosphere.

[0039] 1. Test whether arbutin can guide zinc ions to be uniformly deposited on the surface of the negative electrode zinc sheet.

[0040] The LANDCT3004A Blue Battery Testing System was used to test batteries at different current densities (mA·cm). -2 ) and area capacity (mA·h·cm -2 Cyclic stability of Zn||Zn symmetric cells assembled under the following conditions.

[0041] Figure 1 A Zn||Zn symmetric cell prepared using the electrolyte of Comparative Example 1 was tested at 1 mA·cm⁻¹. -2 Current density and 1 mA·h·cm -2 Cyclic charge-discharge curves at deposition capacity; Figure 2 , Figure 3 , Figure 4 Zn||Zn symmetric cells prepared using the electrolyte of Example 1 were tested at 1 mA·cm⁻¹. -2 Current density and 1 mA·h·cm -2 At deposition capacity, 10 mA·cm -2 Current density and 1 mA·h·cm -2 At deposition capacity, 5 mA·cm -2 Current density and 1 mA·h·cm -2 Cyclic charge-discharge curves at deposition capacity. It can be seen that when arbutin is present in the electrolyte, the Zn||Zn symmetric battery exhibits superior stability and a significantly improved lifespan during cycling.

[0042] 2. To test the inhibitory effect of arbutin on hydrogen evolution side reaction during the charging and discharging process of aqueous zinc-ion batteries.

[0043] In the electrolytes of Example 1 and Comparative Example 1, the hydrogen evolution potential was measured in zinc / / titanium batteries using linear sweep voltammetry (LSV) on an electrochemical workstation CHI 760F at a scan rate of 1 mV / s.

[0044] The hydrogen evolution test results of Example 1 and Comparative Example 1 are as follows: Figure 5 As shown, the hydrogen evolution potential window of the aqueous zinc-ion battery electrolyte in Example 1 is larger than that in Comparative Example 1, indicating that the addition of arbutin can inhibit the decomposition of water.

[0045] 3. To test the effect of arbutin on dendrite growth during the charging and discharging process of aqueous zinc-ion batteries.

[0046] The Zn||Zn symmetric cells assembled with the electrolytes prepared in Example 1 and Comparative Example 1 were tested using the chronoamperometry method. The test results are as follows: Figure 6As shown, in the comparative example, the current density increased linearly within 1000 s, indicating that zinc deposition expanded with dendrite growth, while Example 1 showed a stable current, indicating that the addition of arbutin to the electrolyte can limit the self-diffusion of Zn ions.

[0047] In summary, the arbutin additive provided by this invention is characterized by its simple synthesis, low cost, environmental friendliness, and scalability. Furthermore, the arbutin additive can guide homogeneous zinc ion deposition, significantly inhibiting side reactions and dendrite growth. Moreover, the aqueous zinc-ion battery electrolyte formulated with the arbutin additive effectively solves problems such as short circuits caused by dendrite growth in aqueous zinc-ion batteries, significantly improving their cycle stability. Therefore, the arbutin additive provided by this invention has great application potential in suppressing side reactions and optimizing zinc deposition, contributing to the development of a high-performance aqueous zinc-ion battery with promising energy storage applications.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the specific implementation of the present invention. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. An aqueous zinc-ion battery electrolyte based on arbutin, characterized in that, The zinc-ion battery electrolyte comprises the following components: Zinc salt, arbutin, solvent.

2. The arbutin-based aqueous zinc-ion battery electrolyte according to claim 1, characterized in that, The zinc salt includes one or more of ZnSO4, ZnCl2 and Zn(OTf)2; The solvent is water.

3. The arbutin-based aqueous zinc-ion battery electrolyte according to claim 1, characterized in that, The mass concentration of arbutin in the zinc-ion battery electrolyte is 0.1%~1%.

4. The arbutin-based aqueous zinc-ion battery electrolyte according to claim 1, characterized in that, The concentration of zinc salt in the zinc-ion battery electrolyte is 0.1~4 mol / L.

5. A method for preparing an arbutin-based aqueous zinc-ion battery electrolyte according to any one of claims 1 to 4, characterized in that, Includes the following steps: The arbutin-based aqueous zinc-ion battery electrolyte is obtained by mixing zinc salt, arbutin and solvent and then sonicating.

6. The method for preparing an aqueous zinc-ion battery electrolyte based on arbutin according to claim 5, characterized in that, The temperature of the ultrasound is 20~30℃, and the duration is 5~15min.

7. The application of an arbutin-based aqueous zinc-ion battery electrolyte as described in any one of claims 1 to 4 in zinc-ion batteries.

8. The application of the arbutin-based aqueous zinc-ion battery electrolyte according to claim 7 in zinc-ion batteries, characterized in that, The zinc-ion battery includes a positive electrode, a negative electrode, and an arbutin-based aqueous zinc-ion battery electrolyte.

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