Preparation method and application of one-dimensional zinc ion battery anode interface layer material based on regenerated cellulose

Abstract

The invention discloses a preparation method and application of a one-dimensional zinc ion battery anode interface layer material based on a regenerated cellulose base, and belongs to the field of polymer nano composite materials. The preparation method of the anode interface layer material of the zinc ion battery comprises the following steps: mixing 1-butyl-3-methylimidazolium chloride with cotton pulp to obtain a precursor solution containing regenerated cellulose; and uniformly coating the surfaces of different zinc wires with the obtained precursor solution, washing the zinc wires with distilled water to wash away the ionic liquid in the zinc wires, and forming a regenerated cellulose shell layer on the surfaces of the zinc wires to obtain the zinc ion battery anode material. The regenerated cellulose is prepared by taking the cotton pulp and the ionic liquid as raw materials, and the corresponding preparation scheme is optimized, so that the product can be endowed with a unique nano structure. Through molecular chain rearrangement and composite functional design, the regenerated cellulose interface layer realizes collaborative optimization of an amorphous-porous composite structure and high mechanical flexibility. The zinc wire battery has high mechanical strength, chemical stability and a functional surface, provides an efficient ion transmission path and dendritic crystal inhibition capability for the zinc wire battery, and remarkably improves the performance and the service life of the battery.

Description

Technical Field

[0001] The present invention relates to the field of polymer nanocomposite materials, and in particular to a preparation method and application of a one-dimensional zinc ion battery anode interface layer material based on regenerated cellulose. Background Art

[0002] Aqueous zinc-ion batteries (Zn-ion batteries), with their high theoretical capacity of 820 mAh / g and low redox potential of -0.762 V (vs. SHE) of the Zn anode, have become a key research focus for next-generation energy storage technologies. However, their industrialization is severely hampered by the poor reversibility of the Zn metal anode. This is associated with water-induced parasitic reactions (such as the hydrogen evolution reaction (HER) and Zn corrosion) and dendrite growth, resulting in poor Coulombic efficiency (CE) and unsatisfactory cycle life. To address these issues, approaches such as electrolyte optimization, interface engineering, and structural design have been proposed. Electrolyte optimization eliminates the need to modify the electrode structure, improves the smoothness of Zn ion deposition, and reduces the likelihood of side effects. In terms of interface engineering, various approaches have been proposed, such as interface modification, interface enhancement, and interface regulation. These approaches aim to improve the performance and stability of Zn-ion batteries. For example, interface modification can improve interface properties by changing the interface structure; interface enhancement can enhance interface properties by introducing reinforcing agents; and interface regulation can modulate interface properties by adjusting interface conditions. The combined application of these approaches can enhance the performance and stability of Zn-ion batteries. It can effectively assist in uniformly dispersing zinc ions during the deposition process.

[0003] In order to solve the interfacial stability problem of zinc metal negative electrode in aqueous zinc ion batteries in practical applications, dendrites can be reduced by preparing an interfacial layer, such as polymer-based (PAM coating), inorganic compound-based (zinc phosphate layer), alloy (Zn-Sn-Bi alloy), etc., which provides a uniform deposition space for zinc ions and inhibits the dendrite growth caused by excessive local current density.

[0004] The cellulose molecular chain contains oxygen-containing functional groups, which makes cellulose have good water-locking ability and zinc affinity, which helps to reduce water-induced side reactions and make Zn 2+ Ion homogenization is possible. However, there are risks of water penetration corrosion and ion transport barriers. Therefore, it is necessary to obtain regenerated cellulose with low crystallinity to prepare the interface layer, because low crystallinity allows for more free active hydroxyl groups. Therefore, how to reduce its crystallinity by improving the preparation method, time, and temperature of regenerated cellulose, and how to change the diameter of the zinc filament after coating to improve electrochemical performance and reduce dendrites are the keys to preparing high-performance zinc-ion batteries. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing a one-dimensional zinc ion battery anode interface layer material based on regenerated cellulose and its application, so as to solve the above-mentioned problems in the background technology. The present invention uses 1-butyl-3-methylimidazolium chloride and cotton pulp as raw materials and optimizes the corresponding preparation method of regenerated cellulose. Through molecular chain rearrangement and composite functionalization design, the regenerated cellulose interface layer achieves the synergistic optimization of amorphous-porous composite structure and high mechanical flexibility. The increase in free and exposed active hydroxyl groups regulates the zinc deposition kinetics and constructs a solid electrolyte interface. The regenerated cellulose interface layer prepared by ionic liquid significantly promotes the Zn 2+ The uniform nucleation of the cells can be achieved, which inhibits the growth of dendrites and the continuous decomposition of the electrolyte, reducing the occurrence of side reactions and having a positive impact on improving the coulombic efficiency of the battery and extending the cycle life.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention is to provide a method for preparing a one-dimensional zinc ion battery anode interface layer material, comprising the following steps:

[0008] mixing 1-butyl-3-methylimidazolium chloride with cotton pulp to obtain a precursor solution containing regenerated cellulose;

[0009] The obtained precursor solution is evenly coated on the surface of different zinc wires, which are then rinsed with distilled water to remove the ionic liquid, and a regenerated cellulose shell layer is formed on the surface of the zinc wire to obtain the zinc ion battery anode material.

[0010] Preferably, 1-butyl-3-methylimidazolium chloride is mixed with cotton pulp to obtain a precursor solution containing regenerated cellulose.

[0011] Preferably, the mixing temperature of the mixing and cooking is 80° C., and the total heating time is 120 min.

[0012] The mechanical stirring of the present invention can improve dispersibility and uniformity.

[0013] Preferably, the diameter of the zinc wire is in the range of 0.3-0.8 mm; and the concentration of the 1-butyl-3-methylimidazolium chloride is ≥98%.

[0014] Preferably, the cotton pulp is fully dispersed by a stirrer and then placed in an oven at 60° C. for 24 hours.

[0015] Preferably, the 1-butyl-3-methylimidazolium chloride needs to be sealed and stored in a dry environment due to its strong hygroscopic properties.

[0016] The second technical solution of the present invention is to provide a one-dimensional zinc ion battery anode interface layer material obtained according to the above preparation method.

[0017] Preferably, the zinc wire material needs to be sanded first to remove the oxide layer on the surface of the wire, and then cleaned with ethanol to remove dust and tiny particles generated by grinding. Ethanol evaporates quickly, reducing moisture residue and avoiding metal oxidation or corrosion.

[0018] Preferably, the one-dimensional anode interface layer material of the zinc ion battery needs to be applied on the surface of the zinc wire by brushing.

[0019] Preferably, after the one-dimensional anode interface layer material of the zinc ion battery is coated on the surface of the zinc wire, the surface needs to be rinsed with distilled water as soon as possible to wash away the ionic liquid, and then soaked in distilled water for 6 hours to remove residual ionic liquid.

[0020] Preferably, the one-dimensional anode needs to be dried in a vacuum drying oven to remove surface moisture.

[0021] Preferably, the vacuum drying oven setting parameters are: temperature 40°C, vacuum degree 0.1kPa, time 2h.

[0022] The third technical solution of the present invention is to provide a one-dimensional cathode material for a zinc ion battery.

[0023] Preferably, the nickel wire material needs to be sanded first to remove the oxide layer on the surface of the wire, and then cleaned with ethanol to remove dust and tiny particles generated by grinding. Ethanol evaporates quickly, reducing moisture residue and avoiding metal oxidation or corrosion.

[0024] Preferably, the γ-manganese dioxide, carbon black and polyvinylidene fluoride are mixed in a ratio of 7:2:1, and N-methylpyrrolidone is added thereto and the mixture is ground in an agate mortar.

[0025] Preferably, the obtained reagent is coated on the surface of the nickel wire.

[0026] Preferably, the one-dimensional cathode material for the zinc ion battery is dried in an oven, wherein the oven setting parameters are: temperature 80° C., time 12 hours.

[0027] The fourth technical solution of the present invention is to provide an application of the above-mentioned one-dimensional anode interface layer material of zinc ion battery in the preparation of zinc ion battery.

[0028] Preferably, the zinc ion battery is a symmetrical battery and a full battery.

[0029] The technical principles of the present invention are as follows:

[0030] The invention prepares a one-dimensional zinc ion battery anode material by adjusting the diameter of the zinc wire and the heating time of cotton pulp and 1-butyl-3-methylimidazolium chloride in a water bath and brushing the zinc wire after heating to form an interface layer on the surface of the zinc wire through the action of hydrogen bonds.

[0031] Compared with the traditional scheme using cellulose as raw material, the present invention uses ionic liquid method to prepare regenerated cellulose as the interface layer, which can increase more free and exposed active hydroxyl groups as zinc-philic sites, and adsorb Zn through electrostatic interaction or coordination bond. 2+ , promoting uniform nucleation. And the regenerated cellulose interface layer achieves the synergistic optimization of amorphous-porous composite structure and high mechanical flexibility.

[0032] The present invention has found through experiments that by adjusting the stirring time in the water bath, the obtained regenerated cellulose has a higher crystallinity as determined by XRD testing.

[0033] Furthermore, the concentration of cellulose in the present invention also needs to be specifically limited. When the concentration is higher than 1%, the concentration of the product is high and coating is difficult.

[0034] When the one-dimensional zinc ion battery anode material of the present invention is prepared into a symmetrical battery, the cycle efficiency over 800 hours is 100%.

[0035] The beneficial technical effects of the present invention are as follows:

[0036] The present invention uses 1-butyl-3-methylimidazolium chloride and cotton pulp as raw materials and optimizes the corresponding preparation method of regenerated cellulose. Through molecular chain rearrangement and composite functionalization design, the regenerated cellulose interface layer achieves the synergistic optimization of amorphous-porous composite structure, dense charge shielding layer and high mechanical flexibility. The increase of free and exposed active hydroxyl groups regulates the zinc deposition kinetics and constructs a solid electrolyte interface. The regenerated cellulose interface layer prepared by ionic liquid significantly promotes the Zn 2+ The uniform nucleation of the cells can be achieved, which inhibits the growth of dendrites and the continuous decomposition of the electrolyte, reducing the occurrence of side reactions and having a positive impact on improving the coulombic efficiency of the battery and extending the cycle life. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0038] Figure 1 The planar SEM images of cotton pulp and regenerated cellulose filaments in Example 1 are shown in Figure 1. a: cotton pulp, b: regenerated cellulose prepared using ionic liquid.

[0039] Figure 2 This is a cross-sectional SEM image of the regenerated cellulose coated on the zinc wire in Example 1.

[0040] Figure 3 SEM images of the anode materials of symmetrical batteries prepared from the products of Examples 3 and 4 and zinc filament after cycling. (a) Pure zinc filament, (b) Regenerated cellulose prepared with DMAC / LiCl as the interface layer, and (c) Regenerated cellulose prepared with ionic liquid as the interface layer.

[0041] Figure 4 This is a schematic diagram of XRD of regenerated cellulose prepared using the ionic liquid of Example 2-3.

[0042] Figure 5 This is a schematic diagram of the cycle efficiency of the symmetrical battery in Example 3 after 750 hours of cycling. DETAILED DESCRIPTION

[0043] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0044] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or stated range, and any other stated value or intervening value in the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention.

[0046] The terms “include,” “including,” “have,” “contain,” etc. used in the present invention are open-ended terms, meaning including but not limited to.

[0047] The diameter of the zinc wire used in the following embodiments and comparative examples of the present invention is in the range of 0.3-0.8 mm, and the diameter of the nickel wire is in the range of 0.3-0.8 mm.

[0048] The raw materials used in the following examples and comparative examples of the present invention are all commercially available products.

[0049] Example 1

[0050] A method for preparing a one-dimensional zinc ion battery anode interface layer material:

[0051] 0.1 g of cotton pulp and 10 g of 1-butyl-3-methylimidazolium chloride (cellulose content: 1%) were stirred and heated in a water bath (80°C for 40 min) to obtain a precursor solution. The precursor solution containing regenerated cellulose was coated on the surface of a polished zinc wire (0.3 mm in diameter), rinsed with distilled water to remove the ionic liquid, and then dried in a vacuum oven (40°C, 0.1 kPa, for 2 h) to form a regenerated cellulose shell.

[0052] Figure 1 This is the SEM image of the cotton pulp material in Example 1.

[0053] Figure 1 This is the SEM image of the regenerated cellulose film material in Example 1.

[0054] Depend on Figure 1 It can be seen that the cotton pulp material in Example 1 is composed of interwoven cellulose, while the artificial interface of the treated regenerated cellulose presents a smooth and dense texture.

[0055] Example 2

[0056] A method for preparing a one-dimensional zinc ion battery anode material:

[0057] 0.1 g of cotton pulp and 10 g of 1-butyl-3-methylimidazolium chloride (cellulose content: 1%) were stirred and heated in a water bath (80°C for 120 min) to obtain a precursor solution. The precursor solution containing regenerated cellulose was coated on the surface of a polished zinc wire (0.3 mm in diameter), rinsed with distilled water to remove the ionic liquid, and then dried in a vacuum oven (40°C, 0.1 kPa, for 2 h) to form a regenerated cellulose shell.

[0058] The regenerated cellulose material prepared in Example 2 was analyzed by XRD test, and it was found that its crystallinity was 24.6%, which was significantly lower than the crystallinity of cotton pulp (63.72%).

[0059] Example 3

[0060] A method for preparing a one-dimensional zinc ion battery anode material:

[0061] 0.1 g of cotton pulp and 10 g of 1-butyl-3-methylimidazolium chloride (cellulose content: 1%) were stirred and heated in a water bath (80°C for 120 min) to obtain a precursor solution. The precursor solution containing regenerated cellulose was coated on the surface of a polished zinc wire (0.5 mm in diameter), rinsed with distilled water to remove the ionic liquid, and then dried in a vacuum oven (40°C, 0.1 kPa, for 2 h) to form a regenerated cellulose shell.

[0062] The one-dimensional zinc-ion battery anode material prepared in Example 3 was analyzed using cyclic voltammetry (CV) curves to study its kinetic behavior. The CV curves were found to be consistent with the GCD profile. Furthermore, as the scan rate increased, the peak current increased accordingly, and the CV curve maintained its integrity.

[0063] Example 4

[0064] A method for preparing a one-dimensional zinc ion battery anode material:

[0065] 0.9 g of cotton pulp, 27.6 mL of N,N-dimethylacetamide (DMAc), and 2.4 g of lithium chloride (LiCl) (containing 3% cellulose) were stirred and heated in a water bath (80°C for 120 min) to obtain a precursor solution. The precursor solution containing regenerated cellulose was then coated on the surface of a polished zinc wire (0.5 mm in diameter). The wire was first placed in an 80°C oven to evaporate the DMAC, and then rinsed with distilled water to remove the LiCl, forming a regenerated cellulose shell.

[0066] By observing the one-dimensional zinc ion battery anode material of the regenerated cellulose interface layer prepared in Example 4 before and after cycling, it was clearly found that dendrites were generated at the zinc ion battery anode after cycling.

[0067] Effect verification

[0068] 1. Perform XRD on the one-dimensional zinc ion battery anode interface layer material prepared in Example 2.

[0069] Figure 4 This is a schematic diagram of the XRD of the interface layer material of the zinc ion battery anode material in Example 2.

[0070] Depend on Figure 2 It can be seen that after the test, the crystallinity of the product is significantly reduced.

[0071] 2. The zinc ion battery anode materials of each embodiment and comparative example were assembled into batteries, and their corresponding electrochemical properties were tested.

[0072] Assembly of symmetrical batteries:

[0073] A symmetrical cell was assembled using two one-dimensional zinc-ion battery anode materials (ICs) as electrodes and 0.2M ZnSO₄ as the electrolyte in a 200mL non-sealed electrolytic cell. Prior to electrochemical testing, the assembled cell was exposed to air for 10 hours to stabilize its performance and facilitate testing.

[0074] Assembly of aqueous zinc-ion batteries (Azibs):

[0075] To prepare the cathode, a slurry consisting of γ-MnO2 (70 wt%), carbon black (20 wt%), and polyvinylidene fluoride (PVDF) (10 wt%) dispersed in N-methylpyrrolidone was coated onto nickel wires of varying diameters and then dried at 80°C for 24 hours. Full cells were assembled using an IC as the anode, a glass cellulose membrane approximately 19 mm in diameter as the separator, and a mixed aqueous solution containing 0.2 M ZnSO4 and 2 M MnSO4 as the electrolyte. 150 mL of the electrolyte was added to each aqueous zinc ion full cell.

[0076] Depend on Figure 5 It can be seen that when the current density is stable at 0.5mA / cm 2 When the cycle was continued for 750 h, the voltage of the product of Example 3 was stable, while in other examples, the voltage fluctuated significantly. This may be because other products would produce a large number of dendrites during the cycle. Figure 3 a is a SEM diagram of a zinc wire with a diameter of 0.5 mm. Figure 3 b is a SEM diagram of DMAC / LiCl as the interface layer of zinc wire. Figure 3 c is a SEM diagram of the zinc wire with ionic liquid as the interface layer).

[0077] Depend on Figure 5 It can be seen that the one-dimensional zinc ion battery anode material prepared in Example 3 has the best cycle efficiency and cycle stability when assembled into a symmetrical battery compared with the products of other examples.

[0078] In summary, the product of the present invention promotes the 2+ The uniform nucleation of the electrolyte inhibits dendrite growth and the continuous decomposition of the electrolyte, reducing the occurrence of side reactions, which has a positive impact on improving the coulombic efficiency and extending the cycle life of the battery. Tests have shown that batteries prepared with the product of the present invention have high coulombic efficiency, good battery cycle performance and reversibility, and no obvious polarization during the charge and discharge process.

[0079] The other interface layers and the anodes without interface layers deformed to varying degrees after cycling. After cycling, the surface of the product in Example 3 was smooth, and the SEM images showed that dendrite-free Zn deposition and growth were achieved, while the surface of the other zinc filaments was broken, and lamellar dendrites grew on a large scale, and the surface became relatively rough and thickened. The regenerated cellulose prepared from low-crystallinity ionic liquids constructed a stable electrode / electrolyte interface by optimizing structural flexibility, interfacial ion transport, and surface uniformity, effectively suppressing zinc dendrites.

[0080] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for preparing a one-dimensional zinc ion battery anode interface layer material, characterized in that: The following steps are involved: Cotton pulp and 1-butyl-3-methylimidazolium chloride are reacted to obtain a precursor solution containing regenerated cellulose; The obtained precursor solution is evenly coated on the surface of different zinc wires, which are then rinsed with distilled water to remove the ionic liquid, and a regenerated cellulose shell layer is formed on the surface of the zinc wire to obtain the zinc ion battery anode material.

2. The preparation method according to claim 1, characterized in that The diameter of the zinc wire is in the range of 0.3-0.8 mm; the diameter of the nickel wire is in the range of 0.3-0.8 mm; and the concentration of the 1-butyl-3-methylimidazolium chloride is ≥98%.

3. The preparation method according to claim 1, characterized in that The 1-butyl-3-methylimidazolium chloride has strong hygroscopic properties and needs to be sealed and stored in a dry environment.

4. The preparation method according to claim 3, characterized in that After the cotton pulp is fully dispersed by a stirrer, it needs to be placed in a 60°C oven for drying for 24 hours.

5. The preparation method according to claim 1, characterized in that The mixing temperature of the mixing and cooking is 80° C., the mechanical stirring speed is , and the total heating time is 120 min.

6. The preparation method according to claim 1, characterized in that The zinc wire material needs to be polished with sandpaper first to remove the oxide layer on the surface of the wire, and then cleaned with ethanol to remove dust and tiny particles generated by polishing. Ethanol evaporates quickly, reducing moisture residue and avoiding metal oxidation or corrosion.

7. The preparation method according to claim 1, characterized in that The one-dimensional anode interface layer material of the zinc ion battery needs to be applied on the surface of the zinc wire by brushing.

8. A one-dimensional zinc ion battery anode material obtained according to the preparation method according to any one of claims 1 to 7.

9. The zinc ion battery anode material according to claim 8, wherein The crystallinity of the zinc ion battery anode material is 24.6%.

10. Use of the zinc ion battery anode material according to claim 8 or 9 in preparing a zinc ion battery.

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