Degradable bio-gel electrolyte and preparation method and use thereof

Abstract

The application discloses a degradable biological gel electrolyte and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing water-washed and dried biological leather into a sealed container, and performing gelation treatment at 55-75 DEG C for 1-3 hours; taking out the biological leather after the gelation treatment, and cleaning the biological leather; adjusting the pH value to 5.0-9.0; and drying for 10-48 hours. Then, the dried biological leather is placed into a prepared electrolyte salt solution to perform ion exchange for 12-48 hours, so as to obtain a biological gel electrolyte material. The biological gel electrolyte material has the advantages of high flexibility, high mechanical strength and degradability, and the preparation method has the characteristics of low production cost, easy scale production and green environmental protection. The assembled flexible energy storage device shows good electrochemical performance, and has a wide prospect in the fields of intelligent clothes, implantable medical devices and artificial electronic skin.

Description

Technical Field

[0001] This invention relates to the field of energy storage, specifically to gel electrolyte materials, and more specifically to a biodegradable biogel electrolyte, its preparation method, and its uses. Background Technology

[0002] In recent years, the rapid development of flexible wearable electronic devices has placed higher demands on the safety and flexibility of energy storage devices. Traditional rigid energy storage devices cannot withstand deformations such as torsion, compression, folding, and stretching, which greatly limits the widespread application and technological innovation of flexible electronic devices. Flexible energy storage devices combine constant power supply and physical flexibility, breaking the constraints of current rigid energy storage device designs, and are widely used in wearable electronic products, foldable displays, and implantable electronic products.

[0003] Electrolytes provide ion transport channels between two electrodes, significantly impacting the power density of flexible energy storage devices. Compared to traditional energy storage devices, solid-state electrolytes offer higher safety, better mechanical stability, and no risk of electrolyte leakage. However, the high crystallinity of all-solid-state electrolytes can hinder ion diffusion rates in flexible energy storage devices, thus reducing conductivity. Therefore, gel electrolytes containing liquid solutions have attracted extensive research. Gel electrolytes often exhibit semi-solid electrolyte characteristics, typically possessing advantages such as high ion mobility, mechanical flexibility, and resistance to damage, making them suitable for flexible wearable electronics.

[0004] Current research on gel electrolytes mostly focuses on polymer gel electrolytes, including polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide (PEO), and polyacrylonitrile (PAN). These are mostly extracted from fossil fuels and, as non-renewable resources, their preparation and degradation result in large amounts of carbon emissions. Summary of the Invention

[0005] In view of this, the present invention provides a biodegradable biogel electrolyte, its preparation method and uses, thereby solving one or more of the above-mentioned problems in the prior art.

[0006] On one hand, the present invention provides a method for preparing a biodegradable biogel electrolyte, comprising the following steps:

[0007] Pretreatment: Cut the bio-leather, wash it with water, and dry it for 10-48 hours;

[0008] Gelation treatment: The pretreated bio-leather is placed in a reactor, and water of 100% to 600% of the leather weight is added. The temperature is adjusted to 55 to 75°C, and then solution A of 100% to 600% of the leather weight is added, or solution A of 100% to 600% of the leather weight is dissolved in water of 100% to 600% of the leather weight. The temperature is adjusted to 55 to 75°C, and the mixture is transferred to the reactor. The reaction is carried out for 1 to 3 hours to gel the leather and obtain bio-gel.

[0009] Post-gelation treatment: Pour out the liquid in the reactor, wash the surface of the biogel, adjust the pH to 5.0-9.0, and dry for 10-48 hours to obtain the biogel electrolyte precursor;

[0010] Ion exchange: The obtained gelled biogel electrolyte precursor is placed in a prepared electrolyte salt solution, the temperature is adjusted to 25-75℃, and it is soaked for 12-48 hours to obtain the biogel electrolyte.

[0011] In some embodiments, the biogel raw material is one or more of cowhide, sheepskin, pigskin, and their derivatives.

[0012] In some embodiments, solution A is one or more of sodium hydroxide solution, hydrogen chloride solution, or hydrogen peroxide solution.

[0013] In some embodiments, the method for drying bio-leather and bio-gel is one or more of the following: natural hanging drying, forced-air drying, freeze drying, vacuum drying, or plate drying.

[0014] In some embodiments, the solute of the electrolyte salt solution is at least one of lithium salt, zinc salt, and sodium salt; the solvent of the electrolyte salt solution is one or more of water, ethanol, ethylene glycol, and dimethyl sulfoxide; and the additive in the electrolyte salt solution is one or more of penetrant JFC, penetrant T, strontium oxalate, and 2,2-dimethylolpropionic acid.

[0015] In some embodiments, the concentration of the electrolyte salt solution is 0.1–10 M.

[0016] In some embodiments, the thickness of the biogel electrolyte is 0.02–3 mm.

[0017] On the other hand, the present invention provides a biodegradable biogel electrolyte prepared by the above method.

[0018] In another aspect, the present invention provides the application of the biodegradable biogel electrolyte obtained by the above method in smart clothing, implantable medical devices or artificial electronic skin.

[0019] In another aspect, the present invention provides the application of biodegradable biogel electrolytes in smart clothing, implantable medical devices, or artificial electronic skin.

[0020] The present invention has the following advantages:

[0021] 1. The biogel electrolyte of the present invention selects bio-leather as the electrolyte material. Leather itself has the advantages of flexibility, high mechanical strength, high ionic conductivity and biodegradability. The preparation method has the characteristics of low production cost, easy large-scale production and green environmental protection.

[0022] 2. The biogel electrolyte of the present invention can significantly improve the ionic conductivity of the gel electrolyte and form a stable ion transport pathway.

[0023] 3. The flexible energy storage device based on the biogel electrolyte of the present invention has the advantages of wide voltage window, high energy density and long service life.

[0024] 4. The biogel electrolyte of the present invention does not show a significant decrease in electrochemical performance after being subjected to one or more physical damages such as bending, hammering, shearing, and perforation.

[0025] 5. The flexible energy storage device based on the biogel electrolyte of the present invention can be well applied to wearable electronic devices. It has the advantages of good biocompatibility, high safety, non-toxicity and harmlessness, and can be worn by users for a long time. Attached Figure Description

[0026] Figure 1 An optical image of the biogel electrolyte material of the present invention;

[0027] Figure 2 This is a schematic diagram illustrating the preparation principle of Example 1 of the present invention;

[0028] Figure 3 An optical image showing the degradation of the biogel electrolyte of the present invention after 45 days under natural soil conditions;

[0029] Figure 4 Test diagram of the damage resistance of the flexible energy storage device assembled with the biogel electrolyte of the present invention;

[0030] Figure 5 The graph shows the ionic conductivity of the biogel electrolyte material prepared in Example 1 of this invention before and after bending. Detailed Implementation

[0031] The present invention will now be described more clearly and completely with reference to the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0032] Example 1

[0033] Preliminary preparation of bio-leather

[0034] First, the softened and de-ashed cowhide is used, then cut, washed, and dried for 10–48 hours.

[0035] Preparation of biodegradable biogel electrolytes, such as Figure 2 As shown:

[0036] Pretreated bio-leather was placed in a reactor, and water (100% by weight of the leather) was added. The temperature was adjusted to 55°C, and then sodium hydroxide solution (100% by weight of the leather) was added. The mixture was transferred to the reactor and reacted for 3 hours. The liquid in the reactor was poured out, the leather surface was washed, the pH was adjusted to 6.0, and the mixture was dried for 48 hours to obtain a biogel electrolyte precursor. Subsequently, the obtained gelled biogel electrolyte precursor was placed in a 3 mol / L zinc sulfate electrolyte solution, and 100% by weight of JFC penetrant (100% by weight of the leather) was added. The pH was adjusted to 6.0 again, and the temperature was adjusted to 55°C. The mixture was soaked for 48 hours to obtain the desired product. Figure 1 The biogel electrolyte material shown.

[0037] The biogel electrolyte prepared by this method has an intrinsic ionic conductivity of 13.6 mS·cm. -1 .

[0038] Example 2

[0039] Preliminary preparation of bio-leather

[0040] First, the de-ashed and softened sheep hides are used, then cut, washed, and dried for 10–48 hours.

[0041] Preparation of biodegradable biogel electrolytes

[0042] Pretreated bio-leather was placed in a reactor, and water (100% of the leather's weight) was added. The temperature was adjusted to 55°C, and then sodium hydroxide solution (100% of the leather's weight) was added. The mixture was transferred to the reactor and reacted for 3 hours. The liquid in the reactor was poured out, the leather surface was washed, the pH was adjusted to 7.0, and the mixture was dried for 48 hours to obtain a biogel electrolyte precursor. Subsequently, the obtained gelled biogel electrolyte precursor was placed in a 4 mol / L zinc chloride electrolyte solution, and sodium dodecyl sulfate (100% of the leather's weight) surfactant was added. The pH was adjusted to 7.0 again, and the temperature was adjusted to 55°C. The mixture was soaked for 48 hours to obtain the biogel electrolyte material.

[0043] The biogel electrolyte prepared by this method has an intrinsic ionic conductivity of 13.5 mS·cm. -1 .

[0044] Example 3:

[0045] Preliminary preparation of bio-leather

[0046] First, the softened and de-ashed bovine top layer leather is used, then cut, washed, and dried for 10–48 hours.

[0047] Preparation of biodegradable biogel electrolytes

[0048] Pretreated bio-leather was placed in a reactor, and water (100% of the leather's weight) was added. The temperature was adjusted to 55°C, and then sodium hydroxide solution (100% of the leather's weight) was added. The mixture was transferred to the reactor and reacted for 3 hours. The liquid in the reactor was poured out, the leather surface was washed, the pH was adjusted to 7.2, and the mixture was dried for 48 hours to obtain a biogel electrolyte precursor. Subsequently, the obtained gelled biogel electrolyte precursor was placed in a 3 mol / L zinc trifluoromethanesulfonate electrolyte solution, and ethanol solution (200% of the leather's weight) was added to the solution. The pH was adjusted again to 7.2, and the temperature was adjusted to 55°C. The mixture was sealed and soaked for 48 hours to obtain the biogel electrolyte material.

[0049] The biogel electrolyte prepared by this method has an intrinsic ionic conductivity of 13.2 mS·cm. -1 .

[0050] Comparative Example 1:

[0051] Preliminary preparation of bio-leather

[0052] First, the softened and de-ashed cowhide is used, then cut, washed, and dried for 10–48 hours.

[0053] Preparation of biodegradable biogel electrolytes

[0054] Pretreated bio-leather was placed in a reactor, and water equal to 100% of the leather's weight was added. The temperature was adjusted to 55°C, and the mixture was transferred to the reactor and reacted for 3 hours. The liquid in the reactor was poured out, the leather surface was washed, the pH was adjusted to 6.0, and the mixture was dried for 48 hours to obtain a biogel electrolyte precursor. Subsequently, the obtained gelled biogel electrolyte precursor was placed in a 2 mol / L zinc sulfate electrolyte solution, the pH was adjusted again to 6.0, and the temperature was adjusted to 55°C for 48 hours to obtain the biogel electrolyte material. The biogel electrolyte prepared by this method has an intrinsic ionic conductivity of 7.8 mS·cm. -1 .

[0055] The difference between Comparative Example 1 and the Examples is that the electrolyte salt solution used in Comparative Example 1 is simply 2 mol / L zinc sulfate without any added organic solvents or surfactants. After soaking, the ions in the electrolyte salt solution cannot fully penetrate into the biogel electrolyte precursor, resulting in limited improvement in the ionic conductivity of the biogel electrolyte material. In the Examples, an additive method is used, allowing the ions in the electrolyte salt solution to fully penetrate into the biogel electrolyte precursor, effectively improving the ionic conductivity of the biogel electrolyte. The same results were also observed with other types of electrolyte salt solutions.

[0056] Performance testing:

[0057] 1. Cut the biogel electrolyte material obtained in Example 1 into 4cm×4cm pieces, bury them 30cm deep in natural soil, and leave them for 45 days.

[0058] Experimental results are as follows Figure 3 As shown, the degradation rate of the biodegradable biogel electrolyte in soil was 50% after 45 days, indicating that the biogel electrolyte material prepared in Example 1 is degradable.

[0059] 2. To test the damage resistance of the biogel electrolyte obtained in the examples, the biogel electrolyte was assembled into a flexible energy storage device, and the assembled flexible energy storage device was subjected to hammering 25 times, bending 500 times, heating and drilling, and the electrochemical performance of the flexible energy storage device after damage was tested.

[0060] Experimental results are as follows Figure 4 As shown, the capacity retention rate did not decrease significantly after being hammered, bent, heated, and punched multiple times.

[0061] 3. The biogel electrolyte prepared in the example was bent 500 times using an electronic universal testing machine, and the ionic conductivity of the biogel electrolyte before and after bending was tested.

[0062] Experimental results are as follows Figure 5As shown, the biogel electrolyte material prepared in Example 1 has an ionic conductivity of 13.6 mS·cm before bending. -1 The self-ionic conductivity after 500 bends is 13.0 mS·cm. -1 This indicates that the biogel electrolyte of Example 1 did not show a significant decrease in its own ionic conductivity after 500 bending physical damage cycles.

[0063] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the inventive concept of the present invention. Equivalent structural transformations made using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are all included within the scope of patent protection of the present invention.

Claims

1. A method for preparing a biodegradable biogel electrolyte, characterized in that, Includes the following steps: Pretreatment: The bio-leather is cut, washed, and dried for 10-48 hours. The bio-leather is one or more of cowhide, sheepskin, and pigskin. Gelation treatment: The pretreated bio-leather is placed in a reactor, water of 100% to 600% of the leather weight is added, the temperature is adjusted to 55 to 75°C, and then solution A of 100% to 600% of the leather weight is added. The mixture is then transferred to the reactor and reacted for 1 to 3 hours to gel the leather and obtain a bio-gel. Solution A is a sodium hydroxide solution. Post-gelation treatment: Pour out the liquid in the reactor, wash the surface of the biogel, adjust the pH to 5.0~9.0, and dry for 10~48h to obtain the biogel electrolyte precursor; Ion exchange: The obtained gelled biogel electrolyte precursor is placed in a prepared electrolyte salt solution, the temperature is adjusted to 25~75℃, and it is soaked for 12~48h to obtain the biogel electrolyte; wherein, the solute of the electrolyte salt solution is at least one of lithium salt, zinc salt, and sodium salt, the solvent of the electrolyte salt solution is one or more of water, ethanol, ethylene glycol, and dimethyl sulfoxide, and the additives in the electrolyte salt solution are one or more of penetrant JFC, penetrant T, strontium oxalate, and 2,2-dimethylolpropionic acid.

2. The method according to claim 1, characterized in that: The drying methods for bio-leather and bio-gel include one or more of the following: natural hanging drying, forced-air drying, freeze drying, vacuum drying, or plate drying.

3. The method according to claim 1, characterized in that: The concentration of the electrolyte salt solution is 0.1~10M.

4. The method according to claim 1, characterized in that, The thickness of the biogel electrolyte is 0.02~3 mm.

5. The biodegradable biogel electrolyte obtained by the method according to any one of claims 1-4.

6. The application of the biodegradable biogel electrolyte obtained by the method according to any one of claims 1-4 in smart clothing, implantable medical devices or artificial electronic skin.

7. The application of the biodegradable biogel electrolyte as described in claim 5 in smart clothing, implantable medical devices, or artificial electronic skin.

Images