Preparation and application of expandable biomass protection film

Abstract

This invention relates to the fabrication and application of a biomass-based, scalable protective film, belonging to the field of zinc-ion battery technology. A transparent black microfluidic liquid is formed by stirring 15 mg / ml carrageenan and 1 mg / ml CNT for 24 hours. 1 ml of this liquid is dropped onto a polished zinc foil and evenly coated using a 100 nm scraper. The foil is then dried in a 60°C oven for 12 hours to obtain a C-CNT@Zn anode. Carrageenan is a negatively charged biomolecule derived from red algae, possessing both environmentally friendly properties and the ability to adsorb Zn. 2+ And repel OH ‑ With SO4 2‑ The presence of anions reduces the occurrence of side reactions. The introduction of CNTs not only significantly improves conductivity but also enhances Zn by constructing a dense interfacial structure. 2+ The concentration of Zn on the zinc surface was effectively increased by this interfacial charge modulation effect. 2+ The local concentration of Zn stabilized the depositional environment. This was achieved by enhancing the interfacial relationship between Zn and the depositional environment. 2+ The adsorption capacity of C-CNT biofilms facilitates uniform zinc deposition and mitigates the occurrence of HER side reactions. Therefore, C-CNT@Zn symmetric cells can achieve a 2 mA cm⁻¹ galvanic cell. ‑2 Achieving an ultra-long cycle life of up to 5500 hours at high current densities, the AZIB demonstrates exceptional stability. This research presents a scalable and efficient strategy aimed at improving the long-term performance of the AZIB in practical energy storage applications.

Description

[0001] Li Li, Qian Ji, Yan Jin, Chen Renjie, Wang Yirui, Xue Tianyang, Chen Yi, Li Yao Technical Field

[0002] This invention relates to the fabrication and application of a biomass-derived, scalable protective film, belonging to the field of zinc-ion battery technology. Background Technology

[0003] Due to the energy crisis and environmental pollution caused by fossil fuel combustion, lithium-ion batteries emerged. As a stable and efficient electrochemical energy storage device, lithium-ion batteries are widely used in various fields such as new energy vehicles, mobile devices, and intelligent robots. However, with increasing attention to environmental issues and battery safety, exploring new green, safe, and stable rechargeable battery systems is crucial. Therefore, zinc-ion batteries have gradually gained attention. Zinc-ion batteries have the following advantages: 1. Low cost and environmentally friendly, with inexpensive raw materials and manufacturing processes; 2. High volumetric capacity (5885 mAh / cm³). -3 It possesses a moderate redox potential (-0.763V vs. standard potential SHE); hydrated zinc ions exhibit a smaller radius and faster conductivity; and it has the potential for large-scale energy storage. Furthermore, aqueous zinc-ion batteries can, to some extent, fill the industry gaps in lithium-ion batteries and supercapacitors. The world's first zinc-ion battery factory has been built in Sweden and is expected to be operational in 2026. Domestic energy storage companies are also actively deploying pilot production lines for zinc-ion batteries to further promote their industrial application.

[0004] Despite the numerous advantages of zinc metal anodes, their application faces significant challenges. The main issues related to zinc metal anodes are as follows: 1. Zn / Zn 2+ The standard electrode potential is lower than H2 / H + The thermodynamic instability of zinc in aqueous electrolytes leads to hydrogen evolution reaction (HER) and chemical corrosion. Due to the uneven distribution of zinc ion flux and electric field at the electrode-electrolyte interface, zinc ions form rough and uneven deposits, promoting dendrite growth. Zn has a high Young's modulus (EZn≈108GPa), and Zn dendrites are more prone to proliferation. This means that once Zn dendrites form, they grow rapidly, leading to irreversible failure or even battery short circuits caused by separator breakdown.

[0005] Reconstructing the Helmholtz layer structure to regulate interfacial chemistry has been considered a key strategy for improving the reversibility of zinc anodes. Current research has confirmed that the behavior of active water molecules in the inner Helmholtz layer (IHP) can be modulated by adsorbing electrolyte additives onto the electrode surface; simultaneously, rare earth (RE) elements, due to their unique electronic structures, can enhance interfacial performance through heterogeneity. Although these strategies have achieved some success in suppressing dendrites and corrosion, achieving a highly stable zinc anode remains a key research objective. Considering cost control and carbon neutrality, biomass materials and a simple experimental preparation process are undoubtedly among the most promising solutions for the industrialization of zinc-in-the-blank (ZIB).

[0006] Inspired by this, we constructed a carrageenan-carbon nanotube (C-CNT) interface layer on a zinc anode using an extremely simple physical coating method. Carrageenan is a negatively charged biomolecule derived from red algae, possessing both environmentally friendly properties and the ability to facilitate Zn adsorption. 2+ It also repels anions such as OH- and SO42-, thereby reducing the occurrence of side reactions. The introduction of carbon nanotubes (CNTs) not only significantly improves conductivity but also enhances Zn by constructing a dense interfacial structure. 2+ The concentration of Zn on the zinc surface was effectively increased by this interfacial charge modulation effect. 2+ The local concentration of Zn stabilized the depositional environment. This was achieved by enhancing the interfacial relationship between Zn and the depositional environment. 2+ The adsorption capacity of C-CNT biofilms facilitates uniform zinc deposition and mitigates the occurrence of HER side reactions. Summary of the Invention

[0007] In view of this, the purpose of this invention is to provide a biomass-derived, scalable interface layer fabrication and its application in aqueous zinc batteries.

[0008] To achieve the above objectives, the technical solution of the present invention is as follows:

[0009] A biomass-derived, scalable interface layer, the material being prepared by the following method, the steps of which are as follows:

[0010] 1. Disperse CNTs in deionized water, preferably 1 mg / ml of CNTs, and stir for 24 hours to form a black suspension;

[0011] 2. Stir the carrageenan and CNT suspension evenly, preferably with 15 mg / ml carrageenan, and stir for 24 hours to form a transparent black micro-flowing liquid;

[0012] 3. Take the well-mixed liquid and apply it to the polished zinc foil. The preferred conditions are: 100-500 μl of C-CNT liquid is dropped onto the polished zinc foil and evenly applied using a 100 nm scraper.

[0013] 4. Then, it was placed in a 60℃ oven and dried for 12 hours to obtain the C-CNT@Zn electrode;

[0014] In a first aspect, the present invention provides a method for preparing a biomass-derived interface layer modified zinc metal electrode, comprising the following steps:

[0015] The negatively charged material was dispersed in deionized water and stirred to obtain a suspension;

[0016] Negatively charged materials include any one of CNTs, graphite, graphene, and MXenes.

[0017] The interfacial raw materials are dispersed in a solution containing a negatively charged material and stirred to obtain a viscous slurry;

[0018] The interface material includes any one of carrageenan (κ, ι, λ type), glycosaminoglycans (GAGs), and Nafion.

[0019] The biomass-derived solution prepared by the above method is coated onto the surface of a zinc metal electrode. After the solvent evaporates, a biofilm-derived interface layer modified zinc metal electrode is obtained.

[0020] Preferably, the method for preparing the polymer interface layer modified zinc metal electrode involves coating 100-500 μl of biofilm solution onto the surface of the zinc metal electrode.

[0021] And / or, the coating method includes any one of the following: casting, spin coating, and pressing.

[0022] Secondly, the present invention also provides a method for preparing a biomass solution, comprising the following steps:

[0023] The negatively charged material was dispersed in deionized water and stirred to obtain a suspension;

[0024] Negatively charged materials include any one of CNTs, graphite, graphene, and MXenes.

[0025] The interfacial raw materials are dispersed in a solution containing a negatively charged material and stirred to obtain a viscous slurry;

[0026] The interface material includes any one of carrageenan (κ, ι, λ type), glycosaminoglycans (GAGs), and Nafion.

[0027] The biofilm solution prepared by the above method is coated onto the surface of the diaphragm, and after the solvent evaporates, a biomass-derived membrane modified diaphragm is obtained.

[0028] Preferably, the method for preparing the carrageenan-modified diaphragm involves coating 5 ml of carrageenan solution onto the diaphragm surface.

[0029] And / or, the diaphragm includes any one of glass fiber or PP diaphragm;

[0030] And / or, the biofilm solution is coated onto the membrane surface, and the solvent is evaporated at room temperature to obtain a biofilm-modified membrane;

[0031] And / or, the coating method includes any one of the following: casting, spin coating, and blade coating.

[0032] Thirdly, the present invention also provides the application of the biological clock membrane as an aqueous zinc electrode interface modification layer in zinc-ion batteries, wherein the zinc-ion batteries include zinc-ion symmetric batteries and / or zinc-ion full batteries.

[0033] Fourthly, the present invention also provides a zinc-ion battery, the zinc-ion battery comprising a zinc-ion symmetric battery and / or a zinc-ion full battery;

[0034] The zinc-ion symmetric battery includes a biomass-coated zinc negative electrode, a biomass-coated zinc positive electrode, and a separator.

[0035] The zinc-ion full battery includes a biomass-coated zinc negative electrode, a positive electrode, a separator, and an electrolyte;

[0036] Beneficial effects

[0037] 1. The biomass-derived solution of the present invention is derived from red algae. This solution is used at the solid electrolyte interface between the Zn negative electrode and the electrolyte. This interface layer has advantages such as low cost and scalable application. Moreover, it can effectively solve the reaction between the zinc metal electrode and the electrolyte and the formation of the passivation layer, and inhibit the corrosion of the zinc negative electrode.

[0038] 2. The interface layer formed by the biomass-derived solution of the present invention has a negatively charged interface layer that reconstructs the hydrated zinc ion structure of the zinc-loving and water-poor inner and outer Helmholtz layers.

[0039] 3. Carrageenan is a negatively charged biomolecule derived from red algae. It is not only environmentally friendly but also helps to adsorb Zn. 2+ And repel OH - With SO4 2- The presence of anions reduces the occurrence of side reactions. The introduction of carbon nanotubes (CNTs) not only significantly improves conductivity but also enhances Zn by constructing a dense interfacial structure. 2+ The concentration;

[0040] 4. This invention applies the designed biomembrane to zinc metal anodes and zinc-ion batteries, enhancing the interface for Zn... 2+ With its high adsorption capacity, the C-CNT biofilm facilitates uniform zinc deposition and mitigates the occurrence of HER side reactions, achieving an ultra-long cycle life of up to 5500 hours. Attached Figure Description

[0041] Figure 1 An optical photograph of the biomass-derived interface layer prepared in Example 1.

[0042] Figure 2 The graph shows the corrosion resistance of the biofilms prepared in Example 1 and Comparative Example 1.

[0043] Figure 3 The graph shows the electrochemical cycling performance of the symmetrical cells assembled in Example 1 and Comparative Example 2.

[0044] Figure 4 The graph shows the electrochemical cycling performance of the asymmetric battery assembled in Example 1. Figure 5 The graph shows the electrochemical cycling performance of the symmetrical battery assembled in Example 1 under high current density. Detailed Implementation

[0045] The present invention will be further described in detail below with reference to specific embodiments.

[0046] Example 1

[0047] 15 mg / ml of carrageenan and 1 mg / ml of CNT were stirred for 24 h to form a transparent black micro-flowing liquid; 1 ml was dropped onto the polished zinc foil and evenly coated with a 100 nm scraper, and then placed in a 60 degree oven to dry for 12 h to finally obtain the C-CNT@Zn anode.

[0048] Optical photographs of the biomass-derived interface demonstrate the potential for large-scale production using this method.

[0049] Example 2

[0050] 15 mg / ml of carrageenan and 1 mg / ml of CNT were stirred for 24 h to form a transparent black micro-flowing liquid; 1 ml was dropped onto the polished zinc foil and evenly coated with a 100 nm scraper, and then placed in a 60 degree oven to dry for 12 h to finally obtain the C-CNT@Zn anode.

[0051] XPS test of the biomass-derived interface Figure 2 The results show that -COOH was successfully added to the derivative interface relative to the bulk biomaterial of Example 1.

[0052] Example 3

[0053] The C-CNT@Zn electrode coated above was cut into Φ11.3mm pieces to form a zinc electrode.

[0054] The positive electrode shell was placed on the experimental platform with its inner surface facing upwards. The zinc electrode, biofilm, separator, biofilm, zinc electrode, and gasket were then placed in sequence. The electrolyte was then dripped in to completely wet the separator. The negative electrode shell was then placed on top, and the battery was packaged using a button cell packaging machine to obtain a zinc-symmetric battery. The Tafel test of the zinc-symmetric battery is as follows: Figure 3 As shown, the corrosion current density is 2.056 mA / cm². -2 .

[0055] Example 4

[0056] The C-CNT@Zn electrode coated above was cut into Φ11.3mm pieces to form a zinc electrode.

[0057] The positive electrode shell was placed on the experimental platform with its inner surface facing upwards. The zinc electrode, biomembrane, separator, biomembrane, zinc electrode, and gasket were then placed in sequence. The electrolyte was then dripped in to completely wet the separator. The negative electrode shell was then placed on top, and the battery was packaged using a button cell packaging machine to obtain a zinc-symmetric battery. The cycle life of the zinc-symmetric battery is as follows: Figure 4 As shown, at 2mA·cm -2 Current density and 2 mAh·cm -2 At the area capacity, it can cycle stably for more than 5500 hours.

[0058] Example 5

[0059] The C-CNT@Zn electrode coated above was cut into Φ11.3mm pieces to form a zinc electrode.

[0060] The positive electrode shell was placed on the experimental platform with its inner surface facing upwards. The zinc electrode, biomembrane, separator, biomembrane, zinc electrode, and gasket were then placed in sequence. The electrolyte was then dripped in to completely wet the separator. The negative electrode shell was then placed on top, and the battery was packaged using a button cell packaging machine to obtain a zinc-symmetric battery. The cycle life of the zinc-symmetric battery is as follows: Figure 5 As shown, at 20mA·cm -2 Current density and 5 mAh·cm -2 Under the given area capacity, it can cycle stably for more than 100 hours.

[0061] Comparative Example 1

[0062] Stir 15 mg / ml carrageenan for 24 h to form a transparent microfluidic liquid; take 1 ml and drop it onto the polished zinc foil, use a 100 nm scraper to coat it evenly, and then put it into a 60 degree oven to dry for 12 h to finally obtain the C@Zn anode.

[0063] Comparative Example 2

[0064] The C@Zn electrode coated above was cut into Φ11.3mm pieces. The surface of commercial zinc foil (700μm) was cleaned and cut into Φ11.3mm round pieces to make zinc electrodes.

[0065] The positive electrode shell was placed on the experimental platform with its inner surface facing upwards. The zinc electrode, biofilm, separator, biofilm, zinc electrode, and gasket were then placed in sequence. The electrolyte was then dripped in to completely wet the separator. The negative electrode shell was then placed on top, and the battery was packaged using a button cell packaging machine to obtain a zinc-symmetric battery. The Tafel test of the zinc-symmetric battery is as follows: Figure 3 As shown, the corrosion current density of the C@Zn electrode is 3.784 mA cm⁻¹. -2 The corrosion current density of the Zn electrode is 4.159 mA cm⁻¹. -2 .

[0066] Comparative Example 3

[0067] The biofilm coated above was cut into Φ11.3mm pieces. The surface of commercial zinc foil (100μm) was cleaned and cut into Φ...

[0068] Zinc electrodes are made from 11.3mm round discs.

[0069] The positive electrode shell was placed on the experimental platform with its inner surface facing upwards. The zinc electrode, biomembrane, separator, biomembrane, zinc electrode, and gasket were then placed in sequence. The electrolyte was then dripped in to completely wet the separator. The negative electrode shell was then placed on top, and the battery was packaged using a button cell packaging machine to obtain a zinc-symmetric battery. The cycle life of the zinc-symmetric battery is as follows: Figure 4 As shown, at 2mA·cm -2 Current density and 2 mAh·cm -2 At the area capacity, the Zn electrode only cycled stably for 376 hours, while the C@Zn electrode cycled for 1546 hours.

[0070] In summary, the invention includes, but is not limited to, the above embodiments. Any equivalent substitutions or partial improvements made under the spirit and principles of this invention shall be considered to be within the protection scope of this invention.

Claims

1. A method for fabricating and applying a biomass-derived, scalable protective film, characterized in that, By mixing biomass materials with conductive materials, a uniform functional layer is formed on the surface of zinc metal anode or separator; The biomass reagent is a negatively charged coating material, including any one of carrageenan (κ, ι, λ type), glycosaminoglycans (GAGs), and Nafion. The conductive material includes any one of CNTs, graphite, graphene, and MXenes.

2. The fabrication of a biomass-derived, scalable protective film according to claim 1, characterized in that, It is simple and easy to implement, and can be readily applied on a large scale for commercial use.

3. The fabrication of a biomass-derived, scalable protective film as described in claim 2, characterized in that, The negatively charged interface layer reconstructs the hydrated zinc ion structure of the zinc-loving, water-depleted inner and outer Helmholtz layers, exhibiting good stability.

4. The biomass-derived, scalable protective film according to claim 4, characterized in that, The specific steps include: S1. Clean the metal / diaphragm negative electrode by physical methods, and / or, the coating method includes any one of casting, spin coating, and pressing, and cut it to a suitable size; S2. The material treated above is dried in an oven at 60°C to obtain a negative electrode or membrane with a biomass-derived interface on its surface.

5. The fabrication of a biomass-derived, scalable protective film according to claim 4, characterized in that, The processing method and parameters need to be adjusted depending on the size of the lithium metal used in step S1.

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