Aqueous zinc ion battery electrolyte based on L-xylose and ribose as well as preparation and application of aqueous zinc ion battery electrolyte

Abstract

The invention discloses an aqueous zinc ion battery electrolyte based on L-xylose and ribose as well as preparation and application thereof, and belongs to the technical field of aqueous ion batteries. Zinc salt, L-xylose (L-Xylose) and ribose (Ribose) are used as an electrolyte of the water-based zinc ion battery, and the electrolyte comprises the following components: water-soluble zinc salt, an additive and water; wherein the additives comprise two additives of L-xylose and ribose, and the electrolyte prepared by the invention optimizes the distribution of nucleation sites; a hydrogen bond network formed by hydroxyl groups can stabilize the electrolyte, self-discharge of the battery and growth of zinc dendrites are effectively inhibited, polarization voltage and nucleation overpotential are reduced, and side reaction of an interface is reduced; the system can be compatible with a lead-acid battery production line and is adaptive to a 48 V communication base station; the method can be expanded to zinc metal-based batteries, such as zinc-iodine batteries, zinc-sulfur batteries, zinc-bromine flow batteries and the like, which adopt zinc as negative electrodes, and the efficiency and the service life of the batteries are improved.

Description

Technical Field

[0001] This invention relates to the field of aqueous zinc-ion battery technology, and particularly to aqueous zinc-ion battery electrolytes based on L-xylose and ribose. Background Technology

[0002] Currently, lithium-ion batteries, due to their excellent energy storage performance, have become the representative batteries for clean energy applications. However, lithium-ion battery technology still has significant safety concerns, especially regarding the composition of its organic electrolytes, which presents safety issues such as flammability and poor thermal stability, limiting the development of lithium-ion batteries. Aqueous electrolytes, as alternatives to organic electrolytes, can effectively improve battery safety performance and reduce manufacturing costs. Furthermore, the ionic conductivity of aqueous electrolytes is two orders of magnitude higher than that of organic electrolytes, enabling batteries to achieve higher power densities.

[0003] Current aqueous batteries mainly include aqueous lithium-ion batteries, aqueous sodium-ion batteries, and aqueous zinc-ion batteries. Among these, zinc metal is relatively low-cost, non-toxic, and has a low redox potential. The high-entropy electrolyte of aqueous zinc-ion batteries can suppress battery self-discharge and zinc dendrite formation, effectively reducing polarization voltage and nucleation overpotential, and also reducing corrosion current and increasing corrosion potential. It has significant application potential in areas such as compatibility with lead-acid battery production lines, adaptation to 48V communication bases, low-altitude economy, and robotics. Furthermore, aqueous zinc-ion batteries can be extended to zinc-iodine batteries, zinc-sulfur batteries, and zinc-bromine flow batteries, which use zinc as the negative electrode and are even more suitable for aqueous electrolytes.

[0004] In summary, the high density of zinc and the two-electron reaction involved in the electrochemical reaction enable zinc-ion batteries to have higher volumetric energy density, which has great application prospects and is considered the preferred direction for the next generation of new power batteries and energy storage batteries.

[0005] The current bottlenecks hindering the continued development of zinc metal batteries mainly include poor interfacial contact, which easily leads to the formation of zinc dendrites, puncturing the separator and ultimately causing severe battery short circuits; zinc dendrites also increase the specific surface area of ​​the negative electrode, accelerating the occurrence of corrosion reactions and hydrogen evolution rates, ultimately resulting in lower coulombic efficiency; and excessively high interfacial activity between the electrode and the electrolyte, which causes some side reactions during battery storage or operation, consuming the charge and discharge capacity and reducing electrode reversibility.

[0006] Therefore, in order to improve the above problems, the electrochemical performance of aqueous zinc-ion batteries can be improved by optimizing the electrolyte of aqueous zinc-ion batteries. Summary of the Invention

[0007] This invention provides an aqueous zinc-ion battery electrolyte based on L-xylose and ribose, its preparation, and its application. Using water-soluble zinc salts, L-xylose, and ribose as raw materials, a high-entropy electrolyte specifically designed for aqueous zinc-ion batteries is prepared. This electrolyte is low-cost and low-risk; it effectively inhibits zinc dendrite growth, reduces polarization voltage and nucleation overpotential, minimizes interfacial side reactions, lowers corrosion current, and increases corrosion potential. It is also compatible with lead-acid battery production lines and adapted to 48V communication base stations. Specifically, this is achieved through the following technologies.

[0008] An aqueous zinc-ion battery electrolyte based on L-xylose and ribose, the raw materials of which include: water-soluble zinc salt, L-xylose, ribose, and distilled water;

[0009] In the aqueous zinc-ion battery electrolyte based on L-xylose and ribose, the concentration of the water-soluble zinc salt is 1 to 3 mol / L, the mass fraction of L-xylose is 1 / 10000 to 5 / 10000, and the mass fraction of ribose is 1 / 10000 to 5 / 10000.

[0010] Furthermore, the concentration of the water-soluble zinc salt is 2 mol / L.

[0011] Furthermore, the mass fraction of the L-xylose is 1 / 10000.

[0012] Furthermore, the mass fraction of the ribose is 1 / 10000.

[0013] Furthermore, the water-soluble zinc salt includes, but is not limited to, ZnSO4.

[0014] The aqueous zinc-ion battery electrolyte provided by this invention improves the environment of the zinc anode in the electrolyte by utilizing the electrolyte within the electrolyte. By introducing L-xylose and ribose, hydroxyl groups are introduced. These hydroxyl groups regulate the solvation structure of zinc ions through hydrogen bonding, thereby effectively inhibiting zinc dendrite growth and reducing hydrogen evolution reaction; ultimately, this significantly improves the battery's cycle life and enhances its cycle stability.

[0015] The present invention also provides a method for preparing the above-mentioned aqueous zinc-ion battery electrolyte based on L-xylose and ribose, which is prepared by stirring and dissolving the water-soluble zinc salt, L-xylose and ribose in distilled water.

[0016] Further, the water-soluble zinc salt is added to the distilled water and stirred to dissolve, and L-xylose and ribose are added and stirred evenly.

[0017] This invention also provides applications of the above-mentioned aqueous zinc-ion battery electrolyte based on L-xylose and ribose. Specifically, it is used as an electrolyte to prepare any type of aqueous zinc-ion battery.

[0018] Compared with the prior art, the advantages of the present invention are:

[0019] 1. The high-entropy electrolyte additive of this invention uses conventional pharmaceutical raw materials, and the preparation method is simple and environmentally friendly. It can be obtained through a dissolution method and then applied in aqueous zinc-ion batteries.

[0020] 2. In this invention, the hydroxyl groups in the additive inhibit the generation of byproducts of the hydrogen evolution reaction and suppress the growth of zinc dendrites by changing the desolvation process of zinc ions.

[0021] 3. Zinc-ion batteries using the additives of this invention exhibit significantly improved cycle stability and superior electrochemical performance. Attached Figure Description

[0022] Figure 1 The Fourier transform infrared (FTIR) and Raman spectra of the ZnSO4 + L-xylose + ribose, ZnSO4 electrolyte provided in Example 1 are shown. Figure 1 a represents the Fourier transform infrared spectrum of ZnSO4 + L-xylose + ribose and ZnSO4. Figure 1 b is the Raman spectrum of ZnSO4 + L-xylose + ribose and ZnSO4.

[0023] Figure 2 This invention, in Example 1, includes the preparation of a Zn / / Zn symmetric cell in an electrolyte at 5 mA / cm². 2 Test graphs under current density. Figure 2 a shows the cyclic test graphs using three different electrolytes: ZnSO4 + L-xylose + ribose, ZnSO4 + L-xylose, and ZnSO4 + ribose. Figure 2 b is the capacity-voltage diagram using the ZnSO4 + L-xylose + ribose electrolyte. Figure 2 c is the capacity-voltage diagram using ZnSO4+L-xylose electrolyte. Figure 2 d is the capacity-voltage diagram using ZnSO4+ ribose electrolyte.

[0024] Figure 3 Example 1 of this invention includes the preparation of a Zn / / Cu half-cell with an electrolyte of 5 mA / cm. 2 Test graph at current density. Figure 3 Figure a shows the cycling performance and coulombic efficiency using three different electrolytes: ZnSO4 + L-xylose + ribose, ZnSO4 + L-xylose, and ZnSO4 + ribose. Figure 3 b is the capacity-voltage diagram using ZnSO4 + L-xylose + ribose. Figure 3 c is the capacitance-voltage diagram using ZnSO4 + L-xylose. Figure 3 d is the capacity-voltage diagram using ZnSO4+ribose.

[0025] Figure 4 The electrolyte (NH4) in Example 1 of this invention is included. x Test results for VO3 / / Zn full cells at a current density of 5 A / g and a charge / discharge range of 0.4 V to 1.8 V. Among them, Figure 4 a is a plot showing the specific capacity and coulombic efficiency using ZnSO4 + L-xylose + ribose, ZnSO4 + L-xylose, and ZnSO4 + ribose. Figure 4 b represents the charge-discharge curves for different numbers of revolutions using a ZnSO4 + L-xylose + ribose electrolyte. Figure 4 c represents the charge-discharge curves using ZnSO4+L-xylose electrolyte with different numbers of cycles. Figure 4 d represents the charge-discharge curves with different numbers of revolutions using ZnSO4+ ribose electrolyte.

[0026] Figure 5 For CV plots using different scan rates, where, Figure 5 a is the CV graph using a ZnSO4 + L-xylose + ribose solution with different scan rates. Figure 5 b is the CV graph using ZnSO4 + L-xylose solution at different scan rates. Figure 5 c is the CV plot for different scan rates using ZnSO4 + ribose solution.

[0027] Figure 6 Image showing an LED light illuminated by a battery connected in series using L-xylose and ribose additives.

[0028] Figure 7 Voltage test diagram for batteries connected in series using L-xylose + ribose additives.

[0029] Figure 8 This is a display of the solutions used in this experiment. Detailed Implementation

[0030] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] In some embodiments of the present invention, the provided aqueous zinc-ion battery electrolyte based on L-xylose and ribose comprises water-soluble zinc salt, L-xylose, ribose, and distilled water as raw materials. The concentration of the water-soluble zinc salt is 1-3 mol / L, the mass fraction of the L-xylose is 1 / 10000 to 5 / 10000, and the mass fraction of the ribose is 1 / 10000 to 5 / 10000.

[0032] Optionally, the concentration of the water-soluble zinc salt is 2 mol / L.

[0033] Optionally, the mass fraction of the L-xylose is 1 / 10000.

[0034] Optionally, the mass fraction of the ribose is 1 / 10000.

[0035] In preparing the above-mentioned aqueous zinc-ion battery electrolyte, the water-soluble zinc salt, L-xylose and ribose weighed according to the required amount are stirred and dissolved in the distilled water.

[0036] Optionally, the water-soluble zinc salt is first added to the distilled water and stirred to dissolve, and then L-xylose and ribose are added and stirred until homogeneous.

[0037] Optionally, water-soluble zinc salts include, but are not limited to, ZnSO4.

[0038] The application of the aqueous zinc-ion battery electrolyte provided by the present invention is specifically for use as an electrolyte in the preparation of aqueous zinc-ion batteries.

[0039] It should be understood that aqueous zinc-ion batteries can be constructed using conventional structures in the art or structures disclosed in other literature. For example, an aqueous zinc-ion battery includes a negative electrode, a positive electrode, a separator, and the aforementioned electrolyte.

[0040] Example 1

[0041] The aqueous zinc-ion battery electrolyte provided in this embodiment is prepared by the following method:

[0042] (1) Weigh about 5.7312 g of ZnSO4•7H2O into a beaker, add 10 mL of distilled water to dissolve it, and obtain a ZnSO4 solution with a concentration of 2 mol / L;

[0043] (2) Weigh 1 mg of L-xylose and 1 mg of ribose and add them to the ZnSO4 solution. Stir the solution with a glass rod until the L-xylose and ribose are completely dissolved to prepare an aqueous zinc-ion battery electrolyte (i.e., “ZnSO4+L-xylose+ribose” electrolyte).

[0044] In the final aqueous zinc-ion battery electrolyte, the concentration of ZnSO4 was 2 mol / L, the mass fraction of L-xylose was 1 / 10000, and the mass fraction of ribose was 1 / 10000.

[0045] Example 2

[0046] The aqueous zinc-ion battery electrolyte provided in this embodiment is prepared in a method that is basically the same as that in Example 1. The difference is that the mass fraction of L-xylose in the final aqueous zinc-ion battery electrolyte is 2 / 10000 and the mass fraction of ribose is 1 / 10000.

[0047] Example 3

[0048] The aqueous zinc-ion battery electrolyte provided in this embodiment is prepared in a method that is basically the same as that in Example 1. The difference is that the mass fraction of L-xylose in the final aqueous zinc-ion battery electrolyte is 2 / 10000 and the mass fraction of ribose is 5 / 10000.

[0049] Example 4

[0050] The aqueous zinc-ion battery electrolyte provided in this embodiment is prepared in a method that is basically the same as that in Example 1. The difference is that zinc chloride (ZnCl2) is used as the raw material, and the concentration of ZnCl2 in the final electrolyte is the same as that of ZnSO4 in Example 1.

[0051] Comparative Example 1

[0052] The aqueous zinc-ion battery electrolyte prepared in this comparative example consists only of ZnSO4 and L-xylose, i.e., ZnSO4 + L-xylose electrolyte; the concentration and mass fraction of both are the same as in Example 1.

[0053] Comparative Example 2

[0054] The aqueous zinc-ion battery electrolyte prepared in this comparative example consists only of ZnSO4 and ribose, i.e., ZnSO4 + ribose electrolyte; the concentration and mass fraction of both are the same as in Example 1.

[0055] Comparative Example 3

[0056] The aqueous zinc-ion battery electrolyte prepared in this comparative example consists only of ZnSO4, i.e., a ZnSO4 solution, with the same concentration as in Example 1.

[0057] Test Example: Performance Testing of Aqueous Zinc-ion Battery Electrolytes

[0058] 1. Fourier transform infrared spectroscopy and Raman spectroscopy testing

[0059] The ZnSO4+L-xylose+ribose electrolyte prepared in Example 1, the ZnSO4+L-xylose electrolyte prepared in Comparative Example 1, the "ZnSO4+ribose" electrolyte prepared in Comparative Document 2, and the ZnSO4 solution prepared in Comparative Example 3 were subjected to Fourier transform infrared spectroscopy and Raman spectroscopy tests, respectively.

[0060] The results are as follows Figure 1 As shown. Among them, Figure 1The Fourier transform infrared spectrum of a shows the absorption peaks of ZnSO4 + L-xylose + ribose electrolyte and ZnSO4 corresponding to several functional groups. The peak at 3250 cm⁻¹ is formed by the stretching vibration of OH. OH reacts with Zn 2+ Hydrogen bonds are formed, reducing side reactions and enhancing solution stability; SO4 2- It is a strongly hydrophilic group that can react with Zn. 2+ Coordination is formed through electrostatic attraction, delaying the reaction of Zn. 2+ Rapid reduction avoids tip discharge caused by excessively high local concentration.

[0061] Figure 1 The Raman spectroscopy results for b show absorption peaks corresponding to several functional groups in the ZnSO4 + L-xylose + ribose electrolyte and ZnSO4. The peak at 3400 cm⁻¹ is formed by the stretching vibration of the OH valence bond, which interacts with Zn. 2+ Hydrogen bonds are formed, increasing Zn 2+ The degree of solvation is reduced, the aggregation of ions is decreased, the stability of ZnSO4 is improved, and the growth of zinc dendrites is effectively inhibited.

[0062] 2. Assembly of aqueous zinc-ion batteries

[0063] (1) Preparation of materials

[0064] (NH4) x The preparation method of the positive electrode sheet for VO3 full battery is as follows: ammonium vanadate, acetylene black, and polyvinylidene fluoride, the positive electrode active material, are mixed in a mass ratio of 7:2:1 to form a uniform positive electrode slurry; the positive electrode slurry is coated on a carbon paper substrate and dried to obtain (NH4). x VO3 positive electrode sheet; stamped using a stamping machine with a diameter of 12 mm.

[0065] Additionally, a stamping machine is used to produce zinc and copper sheets with a diameter of 12 mm, zinc sheets with a diameter of 15 mm, and glass fiber diaphragms with a diameter of 16 mm.

[0066] (2) Assemble the battery

[0067] Zn / / Zn symmetric battery: First, a zinc sheet (negative electrode) is placed into the negative electrode shell, and then a glass fiber separator is placed in. Next, the electrolyte from the above examples or comparative examples is dripped in to completely wet the glass fiber separator. Then, a zinc sheet (positive electrode) is placed in. Finally, a spring is placed in, the positive electrode shell is pressed tightly, and the battery is sealed using a battery packaging machine to obtain the finished aqueous zinc-ion battery. That is, for different electrolytes used, Zn / / Zn symmetric batteries were obtained with ZnSO4+L-xylose+ribose electrolyte (Example 1), ZnSO4+L-xylose electrolyte (Comparative Example 1), ZnSO4+ribose electrolyte (Comparative Example 2), and ZnSO4 electrolyte (Comparative Example 3).

[0068] Zn / / Cu half-cell: Using the same method as the Zn / / Zn symmetrical cell, except that the zinc sheet (positive electrode) was replaced with a 12 mm copper sheet, Zn / / Cu half-cells with ZnSO4+L-xylose+ribose electrolyte (Example 1), ZnSO4+L-xylose electrolyte (Comparative Example 1), ZnSO4+ribose electrolyte (Comparative Example 2), and ZnSO4 electrolyte (Comparative Example 3) were obtained respectively.

[0069] (NH4) x VO3 / / Zn full cell: The same method as the Zn / / Zn symmetric cell is used, except that the zinc sheet (positive electrode) is replaced with the (NH4) electrode with a diameter of 12 mm prepared in step (1). x Using VO3 as the positive electrode, ZnSO4+L-xylose+ribose electrolyte (Example 1), ZnSO4+L-xylose electrolyte (Comparative Example 1), ZnSO4+ribose electrolyte (Comparative Example 2), and ZnSO4 electrolyte (Comparative Example 3) were obtained respectively. x VO3 / / Zn full battery.

[0070] 3. Performance testing of aqueous zinc-ion batteries

[0071] (1) Zn / / Zn symmetric cell test

[0072] The assembled Zn / / Zn symmetric cell was tested using a blue electric field testing system. The test result was 5 mA / cm². 2 Current density, 1mAh / cm 2 Under specific capacity conditions, constant current charge-discharge tests were performed. The test was conducted in the following order: rest, constant current charging, rest, and constant current discharging. The rest period was 30 seconds for each test, and the constant current charge-discharge time was 0.2 hours.

[0073] Test results are as follows Figure 2 As shown, under the same test conditions, by Figure 2As can be seen from a, the cycle time is longer and the polarization voltage is lower than that of the battery using ZnSO4+L-xylose+ribose as electrolyte. It exhibits stable cycle performance and can clearly show the advantages of inhibiting the growth of zinc dendrites, reducing polarization voltage, and reducing nucleation overpotential.

[0074] (2) Zn / / Cu half-cell test

[0075] The Zn / / Cu half-cell assembled in step (6) using the two additives was tested on a blue electric field testing system: specifically, at 5 mA / cm 2 At current density, 1 mAh / cm 2 Under specific capacity conditions, constant current charging and discharging are performed.

[0076] like Figure 3 As shown in Figure a, when using ZnSO4 + L-xylose + ribose electrolyte, the coulombic efficiency remains stable at 99.7%, and the cycle life is longer.

[0077] like Figure 3 b、 Figure 3 c and Figure 3 As shown in Figure d, compared to the electrolytes in Comparative Examples 1-3, the battery using the ZnSO4+L-xylose+ribose electrolyte exhibits a lower polarization voltage; this indicates that the electrolyte prepared in Example 1 significantly enhances the polarization voltage. The lower polarization voltage demonstrates that this solution outperforms the battery systems using ZnSO4+L-xylose and ZnSO4+ribose electrolytes in reducing interfacial reaction resistance and improving energy efficiency. The battery using the electrolyte prepared in Example 1 shows reduced dendrite formation on the surface, resulting in better and more stable cycle performance.

[0078] (3) (NH4) x VO3 / Zn Full Battery Test

[0079] The assembled (NH4) x The VO3 / / Zn full cell was tested on the Blue Electric testing system. Specifically, constant current charging and discharging was performed under conditions of a current density of 5 A / g and a charge-discharge range of 0.4-1.8 V.

[0080] like Figure 4 As shown in Figure a, the battery exhibits better cycle stability when using a ZnSO4 + L-xylose + ribose electrolyte.

[0081] Furthermore, we will conduct charge-discharge curve tests on full cells prepared using the electrolytes of Example 1 and Comparative Examples 1-3. The results are as follows... Figure 4As shown in b, the voltage curves using ZnSO4+L-xylose+ribose electrolyte at different cycle numbers all maintain a clear charge-discharge plateau; and as the number of cycles increases, the plateau decays slowly and the polarization voltage is small.

[0082] Furthermore, we will conduct CV tests using a full cell with a ZnSO4 + L-xylose + ribose electrolyte, setting the scan rate from 1-10 mV / s and taking a few cycles. The results are as follows. Figure 5 As shown, the full cell using ZnSO4+L-xylose+ribose electrolyte exhibits a relatively smooth change in peak current with increasing scan rate, high symmetry, stable redox peak positions, and low peak separation, indicating faster charge transport and lower internal resistance. At high scan rates, the capacity remains good, suggesting that its structure is more conducive to ion transport, with rapid zinc ion migration and reversible interfacial reactions, which can suppress battery self-discharge, reduce corrosion current, and increase corrosion potential.

[0083] Furthermore, we connected three full cells in series using a ZnSO4 + L-xylose + ribose electrolyte, charged them, and measured their voltages and whether they could light up an LED. The results are as follows. Figure 6 As shown, it can charge and discharge normally and light up the LED normally.

[0084] In summary, the ZnSO4+L-xylose+ribose electrolyte of this invention was used to prepare symmetrical batteries, half-cells, and full cells. By regulating zinc ion deposition behavior, stabilizing the electrode interface, and optimizing electrochemical reaction kinetics, the cycle performance of the batteries was significantly improved. The aqueous zinc-ion battery electrolyte provided by this invention exhibits excellent electrochemical performance.

[0085] The above detailed embodiments describe the implementation of the present invention; however, the present invention is not limited to the specific details described in the above embodiments. Within the scope of the claims and technical concept of the present invention, various simple modifications and changes can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. An aqueous zinc-ion battery electrolyte based on L-xylose and ribose, characterized in that, Its raw materials include: water-soluble zinc salt, L-xylose, ribose, and distilled water; In the aqueous zinc-ion battery electrolyte based on L-xylose and ribose, the concentration of the water-soluble zinc salt is 1 to 3 mol / L, the mass fraction of L-xylose is 1 / 10000 to 5 / 10000, and the mass fraction of ribose is 1 / 10000 to 5 / 10000.

2. The aqueous zinc-ion battery electrolyte based on L-xylose and ribose according to claim 1, characterized in that, The concentration of the water-soluble zinc salt is 2 mol / L.

3. The aqueous zinc-ion battery electrolyte based on L-xylose and ribose according to claim 1, characterized in that, The mass fraction of L-xylose is 1 / 10000.

4. The aqueous zinc-ion battery electrolyte based on L-xylose and ribose according to claim 1, characterized in that, The mass fraction of the ribose is 1 / 10000.

5. The aqueous zinc-ion battery electrolyte based on L-xylose and ribose according to claim 1, characterized in that, The water-soluble zinc salts include, but are not limited to, ZnSO4.

6. A method for preparing an aqueous zinc-ion battery electrolyte based on L-xylose and ribose as described in any one of claims 1-5, characterized in that, It is prepared by stirring and dissolving the water-soluble zinc salt, L-xylose and ribose in the distilled water.

7. The method for preparing an aqueous zinc-ion battery electrolyte based on L-xylose and ribose according to claim 6, characterized in that, The water-soluble zinc salt was added to the distilled water and stirred until dissolved. L-xylose and ribose were then added and stirred until homogeneous.

8. The application of an aqueous zinc-ion battery electrolyte based on L-xylose and ribose as described in claims 1-5, or an aqueous zinc-ion battery electrolyte based on L-xylose and ribose prepared by the preparation method described in claim 6 or 7.

Images