Mushroom fiber electrode and method of making same

Abstract

The application provides a mushroom fiber electrode and a preparation method thereof, and belongs to the field of fiber-based electronic materials. The preparation method comprises the following steps: firstly, an alkali-extracted mushroom sample is obtained through water bath and alkali bath treatment; then, the alkali-extracted mushroom sample is fully dissolved in a selected dispersant to obtain a mushroom solution with a mass fraction of 0.5% to 35%, and then a conductive functional material is added into the mushroom solution to obtain a mushroom composite spinning solution; the mushroom composite spinning solution is extruded from a spinneret to a coagulation bath through a metering pump to be solidified and drafted to form a primary molded conductive mushroom fiber filament; the primary molded conductive mushroom fiber filament is repeatedly introduced into a displacement bath to be solvent-displaced and further drafted; and the displaced conductive mushroom fiber filament is heat set to remove water to obtain a continuous and uniform conductive mushroom filament fiber with a diameter of 10 to 500 microns. The prepared mushroom fiber electrode has good stability, excellent conductivity, low contact impedance and good tensile property, and has a good application prospect in implantable electronic devices, intelligent wearable sensors and the like.

Description

Technical Field

[0001] This invention relates to the field of fiber-based electronic materials technology, specifically to a mushroom fiber electrode and its preparation method. Background Technology

[0002] Conductive fibers have advantages such as good flexibility, light weight, strong spinnability and weavability, and have great application potential in the field of multifunctional electronic fabrics; while fiber electrodes are an important component of temperature, humidity, pressure, biochemical sensors in multifunctional electronic fabrics, and have a significant impact on the performance, manufacturing process and cost of the devices.

[0003] my country ranks among the world's top producers of mushrooms. The chitin in the cell walls of mushrooms is the second most abundant renewable polymer in nature after cellulose. It has advantages such as biodegradability, biocompatibility, antibacterial properties, and renewability. The fibers made from it after spinning retain its excellent properties and have great potential in the field of textile materials.

[0004] Mushroom fiber is inexpensive, renewable, and biocompatible. The development of mushroom fiber electrodes expands the application areas of mushrooms and provides new ideas for the development of novel flexible electrodes. However, the electrical insulation properties of mushroom fibers make them difficult to utilize directly. To address this issue, this invention provides a mushroom fiber electrode and its preparation method. Summary of the Invention

[0005] This application provides a mushroom fiber electrode and its preparation method, aiming to provide a method for making fiber electrodes using mushrooms as raw materials, and to provide new ideas for expanding conductive regenerated fibers.

[0006] This preparation method involves mixing conductive functional materials with mushrooms to obtain a spinning solution, and then using wet spinning technology to produce continuous, highly conductive, and biocompatible conductive mushroom fiber electrodes. The mushroom fiber electrodes provided by this invention exhibit good stability, excellent conductivity, low contact impedance, and good tensile properties, showing promising application prospects in implantable electronic devices and smart wearable sensors.

[0007] In a first aspect, embodiments of this application provide a method for preparing a mushroom fiber electrode, comprising the following steps:

[0008] S1, the dried and dehydrated mushroom raw materials are treated with water bath and alkali bath, then crushed, stirred, centrifuged and precipitated, and the precipitate is dried to obtain alkali-extracted mushroom samples;

[0009] S2, fully dissolve the alkaline-extracted mushroom sample obtained in step S1 in the dispersant to obtain a mushroom solution with a mass fraction of 0.5%~35%;

[0010] The dispersant is an ionic liquid, or a mixed solvent consisting of an ionic liquid and a co-solvent;

[0011] The ionic liquid is one or more of the following: tris(2-hydroxyethyl)methylammonium acetate, tris(2-hydroxyethyl)methylammonium methanesulfonate, tetrabutylammonium hydroxide, 1-butyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 2-bromo-1-allyl-3-methylimidazolium ([AMIM]Br), 1-butyl-3-methylimidazolium bromide ([BMIM]Br), and methyl 1-ethyl-3-methylimidazolium sulfate ([EMIM]Ms).

[0012] The co-solvent is one or more of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, ethylenediamine, 1,3-dimethyl-2-imidazolinone, and hexamethylphosphoric triamine;

[0013] S3, add conductive functional material to the mushroom solution obtained in step S2, stir and disperse to obtain mushroom composite spinning solution;

[0014] S4. The mushroom composite spinning solution obtained in step S3 is extruded from the spinneret into the coagulation bath by a metering pump to solidify and stretch. The initially formed conductive mushroom fiber filaments are then repeatedly introduced into the displacement bath for solvent displacement and further stretching. The displacement conductive mushroom fiber filaments are then heat-set to remove moisture, dried and wound to obtain continuous and uniform conductive mushroom filament fibers with a diameter of 10~500μm.

[0015] Furthermore, in step S2, the dispersant is a mixed solvent composed of an ionic liquid and a co-solvent; the ionic liquid is one of tris(2-hydroxyethyl)methylammonium acetate ([THEMA][OAc]) or tris(2-hydroxyethyl)methylammonium methanesulfonate ([THEMA][MeSO3]), and the co-solvent is ethylenediamine. By adding the ionic liquid to ethylenediamine (EDA), the additional EDA enhances the hydrogen bonding ability of the IL / EDA mixture, weakens the interchain hydrogen bonds of chitin in mushroom fibers, and facilitates the dissolution of mushroom fibers.

[0016] Alternatively, the ionic liquid is one of tetrabutylammonium hydroxide ([TBA][OH]), 1-butyl-3-methylimidazolium acetate ([C4MIM][OAC]), 1,3-dibutylimidazolium acetate ([C4C1IM][OAc]), 1,3-dimethylimidazolium acetate ([C1MIM][OAc]), 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]), 1-allyl-3-methylimidazolium chloride ([AMIM]Cl), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), and 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl); the cosolvent is one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolinone (DMI), and hexamethylphosphoric triamine (HMPA).

[0017] Furthermore, in step S3, the mass ratio of the mushroom solution to the conductive functional material is 1:(0.05-20).

[0018] Furthermore, the conductive functional material is one or more of the following: P-type conductive polymer, N-type conductive polymer, single-arm carbon nanotube, multi-walled carbon nanotube, graphite, graphene, graphene oxide, reduced graphene oxide, silver nanowire, two-dimensional metal nitrides and carbides (MXene), metal oxide, metal-organic framework (MOF), conductive covalent organic framework (COF), and quantum dots.

[0019] Furthermore, the P-type conductive polymer is one or more of polypyrrole, polyaniline, poly(p-styrene), PEDOT:PSS, poly(3-hexylthiophene), and poly[3-(4-carboxybutyl)thiophene-2,5-diyl].

[0020] The N-type conductive polymer is one or more of the following: polyetherimide (PEI) doped PEDOT:PSS, polybenzimidazole dibenzophenanthrene (BBL), polybenzodifuran dione, poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-stat-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione], and 6H-pyrrolo[3,2-b:4,5-b']bis[1,4]benzothiazine ladder polymer;

[0021] The two-dimensional metal nitride and carbide MXene is Ti3C2T. x Ti2CT x Nb2CT x V2CT x TiVCT x Ti3CNT xV2NT x Nb4C3T, Mo 4 / 3 Y 2 / 3 CT x (Nb, Zn)4C3T x (TiV)2CT x One or more of the following;

[0022] Furthermore, the metal oxide is one or more of molybdenum oxide (MoO2), tin oxide (SnO2), zinc oxide (ZnO), aluminum oxide (Al2O3), aluminum oxide (Al2O3), indium tin oxide (ITO), antimony-doped tin dioxide (ATO), and aluminum-doped zinc oxide (ZAO);

[0023] Furthermore, the metal-organic framework is one or more of zirconium-based metal-organic frameworks, hexaaminotriphenyl nickel, copper catecholate, copper-based metal-organic frameworks, cobalt-based metal-organic frameworks, hexaaminotriphenyl copper, and lanthanide metal-organic frameworks.

[0024] Furthermore, the conductive covalent organic framework is one or more of the following: nitrogen- and sulfur-doped bis(thiazolyl) covalent organic framework, metal tetraphenylporphyrin-based covalent organic framework, nickel phthalocyanine-tetraazacycloene conjugated framework material, 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic framework, and Janus diketone-based highly conductive conjugated covalent organic framework.

[0025] Furthermore, the quantum dot is one or more of carbon quantum dots, perovskite quantum dots, metal oxide quantum dots, or sulfide quantum dots.

[0026] Furthermore, in step S4, the spinneret nozzle shape is circular, hollow, or irregular; the irregular shape can be triangular, trefoil, polygonal, multi-lobed, square, pentagonal, Y-shaped double cross, or flat. Thus, the prepared fiber cross-section can have different shapes.

[0027] Furthermore, in step S4, the coagulation bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution; the coagulation bath temperature is 20℃~150℃; the coagulation bath time is 15min~2h; and the coagulation stretching ratio is 10%~300%.

[0028] Furthermore, in step S4, the displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.

[0029] Furthermore, in step S4, the temperature of the displacement bath is 20℃~150℃; the displacement stretching ratio is 10%~300%; and the displacement bath time is 5min~2h.

[0030] Furthermore, in step S4, the number of replacements is 2 to 5.

[0031] Furthermore, in step S1, during the alkaline bath treatment, the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and the molar concentration of the alkaline solution is 0.05~5 mol / L.

[0032] Secondly, this application provides a mushroom fiber electrode, which is prepared by any of the aforementioned technical solutions.

[0033] This mushroom fiber electrode exhibits good stability, excellent conductivity, low contact impedance, and good tensile properties, making it a promising candidate for applications in implantable electronic devices and smart wearable sensors.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The method for preparing the mushroom fiber electrode provided in this application firstly removes soluble polysaccharides and glycoproteins from the mushroom through water bath pretreatment and alkali bath pretreatment. Then, the mushroom raw material is freeze-dried at -20~-80℃ or dried at 40~100℃ to obtain an alkali-extracted mushroom sample. The alkali-extracted mushroom sample is then fully dissolved in a selected dispersant to obtain a mushroom solution with a mass fraction of 0.5%~35%. Then, a conductive functional material is added to the mushroom solution to obtain a mushroom composite spinning solution. The mushroom composite spinning solution is extruded from the spinneret through a metering pump into a coagulation bath for solidification and stretching. The initially formed conductive mushroom fiber filaments are then repeatedly introduced into a displacement bath for solvent displacement and further stretching. The displacement conductive mushroom fiber filaments are heat-set to remove moisture, resulting in continuous and uniform conductive mushroom filament fibers with a diameter of 10~500μm.

[0036] (2) This application uses mushrooms as raw materials to prepare fiber electrodes. The raw materials are widely available, inexpensive, renewable, energy-saving and biocompatible.

[0037] (3) The mushroom fiber electrode prepared by the present invention has excellent biocompatibility and can provide new methods for the preparation of implantable electronic devices and smart wearable sensors.

[0038] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0039] To more clearly illustrate the technical solution of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0040] Figure 1 The images show actual photos of the mushroom fiber spinning solution and the mushroom / PEDOT:PSS composite spinning solution from Example 1.

[0041] Figure 2 The images show the conductive mushroom fibers prepared in Example 1 and the mushroom fibers prepared in Comparative Example 1.

[0042] Figure 3 The images show the microstructure of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1.

[0043] Figure 4 The infrared spectra of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1 are shown.

[0044] Figure 5 The X-ray diffraction patterns are of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1.

[0045] Figure 6 The electrical properties (resistance) of the mushroom fiber electrode prepared in Example 1 are shown. Detailed Implementation

[0046] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0047] 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 this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0048] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0049] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0050] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0051] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more (including two sets), and "multiple pieces" refers to two or more (including two pieces).

[0052] In the description of the embodiments of this application, unless otherwise expressly specified and limited, technical terms such as "installation," "connection," "joining," and "fixing" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. For those skilled in the art, the specific meaning of the above terms in the embodiments of this application can be understood according to the specific circumstances.

[0053] No method for preparing mushroom fiber electrodes has been disclosed in the existing technology.

[0054] This application provides a method for preparing a mushroom fiber electrode, comprising the following steps:

[0055] S1. The dried and dehydrated mushroom raw materials are treated with a water bath for 0.3-6 h and then with an alkali bath for 0.5-8 h to remove soluble polysaccharides and glycoproteins from the mushrooms. Then, the raw materials are crushed, stirred, centrifuged and precipitated. The precipitate is freeze-dried at -20~-80℃ or dried at 40~100℃ for 24-48 h to obtain alkali-extracted mushroom samples.

[0056] The water bath temperature is 40℃~100℃. The alkali bath temperature is 25℃~100℃.

[0057] During centrifugation sedimentation, the centrifugation speed is 5000 rpm to 20000 rpm, and the centrifugation time is 5 min to 35 min.

[0058] During alkaline bath treatment, the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate.

[0059] The molar concentration of the alkaline solution is 0.05~5 mol / L.

[0060] S2, the alkaline-extracted mushroom sample obtained in step S1 is fully dissolved in the dispersant at a temperature of 85℃~130℃ and a rotation speed of 100rpm~2000rpm to obtain a mushroom solution with a mass fraction of 0.5%~35%.

[0061] The dispersant is an ionic liquid, or a mixed solvent consisting of an ionic liquid and a co-solvent.

[0062] The ionic liquid is one or more of the following: tris(2-hydroxyethyl)methylammonium acetate, tris(2-hydroxyethyl)methylammonium methanesulfonate, tetrabutylammonium hydroxide, 1-butyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 2-bromo-1-allyl-3-methylimidazolium ([AMIM]Br), 1-butyl-3-methylimidazolium bromide ([BMIM]Br), and methyl 1-ethyl-3-methylimidazolium sulfate ([EMIM]Ms).

[0063] When the dispersant is a mixed solvent consisting of an ionic liquid and a co-solvent, the ionic liquid is either tris(2-hydroxyethyl)methylammonium acetate ([THEMA][OAc]) or tris(2-hydroxyethyl)methylammonium methanesulfonate ([THEMA][MeSO3]), and the co-solvent is ethylenediamine. By adding the ionic liquid to ethylenediamine (EDA), the additional EDA enhances the hydrogen bonding ability of the IL / EDA mixture, weakens the interchain hydrogen bonds of chitin in mushroom fibers, and facilitates the dissolution of mushroom fibers.

[0064] Alternatively, the ionic liquid is one of tetrabutylammonium hydroxide ([TBA][OH]), 1-butyl-3-methylimidazolium acetate ([C4MIM][OAC]), 1,3-dibutylimidazolium acetate ([C4C1IM][OAc]), 1,3-dimethylimidazolium acetate ([C1MIM][OAc]), 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]), 1-allyl-3-methylimidazolium chloride ([AMIM]Cl), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), or 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl). The cosolvent is one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolinone (DMI), or hexamethylphosphoric triamine (HMPA).

[0065] S3. Add conductive functional material to the mushroom solution obtained in step S2, stir and disperse to obtain mushroom composite spinning solution.

[0066] The mass ratio of mushroom solution to conductive functional material is 1:(0.05-20).

[0067] The conductive functional material is one or more of the following: P-type conductive polymer, N-type conductive polymer, single-arm carbon nanotube, multi-walled carbon nanotube, graphite, graphene, graphene oxide, reduced graphene oxide, silver nanowire, two-dimensional metal nitrides and carbides (MXene), metal oxide, metal-organic framework (MOF), conductive covalent organic framework (COF), and quantum dot.

[0068] Furthermore, the P-type conductive polymer is one or more of polypyrrole, polyaniline, poly(p-styrene), PEDOT:PSS, poly(3-hexylthiophene), and poly[3-(4-carboxybutyl)thiophene-2,5-diyl]; the N-type conductive polymer is one or more of polyetherimide (PEI) doped PEDOT:PSS, polybenzimidazole dibenzophenanthrene (BBL), polybenzodifurandione, poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-stat-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione], and 6H-pyrrolo[3,2-b:4,5-b']bis[1,4]benzothiazine ladder polymer; and the two-dimensional metal nitride and carbide MXene are Ti3C2T x Ti2CT x Nb2CT x V2CT x TiVCT x Ti3CNT x V2NTx Nb4C3T, Mo 4 / 3 Y 2 / 3 CT x (Nb, Zn)4C3T x (TiV)2CT x One or more of the following;

[0069] Furthermore, the metal oxide is one or more of molybdenum oxide (MoO2), tin oxide (SnO2), zinc oxide (ZnO), aluminum oxide (Al2O3), aluminum oxide (Al2O3), indium tin oxide (ITO), antimony-doped tin dioxide (ATO), and aluminum-doped zinc oxide (ZAO);

[0070] Furthermore, the metal-organic framework is one or more of zirconium-based metal-organic frameworks, hexaaminotriphenyl nickel, copper catecholate, copper-based metal-organic frameworks, cobalt-based metal-organic frameworks, hexaaminotriphenyl copper, and lanthanide metal-organic frameworks.

[0071] Furthermore, the conductive covalent organic framework is one or more of the following: nitrogen- and sulfur-doped bis(thiazolyl) covalent organic framework, metal tetraphenylporphyrin-based covalent organic framework, nickel phthalocyanine-tetraazacycloene conjugated framework material, 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic framework, and Janus diketone-based highly conductive conjugated covalent organic framework.

[0072] S4. The mushroom composite spinning solution obtained in step S3 is extruded from the spinneret into the coagulation bath by a metering pump to solidify and stretch. The initially formed conductive mushroom fiber filaments are then repeatedly introduced into the displacement bath for solvent displacement and further stretching. The displacement conductive mushroom fiber filaments are then heat-set to remove moisture, dried and wound to obtain continuous and uniform conductive mushroom filament fibers with a diameter of 10~500μm.

[0073] The coagulation bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.

[0074] The coagulation bath temperature is 20℃~150℃; the coagulation bath time is 15min~2h; and the coagulation draw ratio is 10%~300%.

[0075] The displacement bath is one or more of the following: deionized water, alcohol, alkaline solution, and metal salt solution.

[0076] The replacement bath temperature is 20℃~150℃; the replacement stretching ratio is 10%~300%; the replacement bath time is 5min~2h. The number of replacements is 2~5 times.

[0077] The spinneret nozzles can be round, hollow, or irregular (triangular, trilobal, polygonal, multi-lobed, square, pentagonal, Y-shaped double cross, flat).

[0078] Secondly, this application provides a mushroom fiber electrode, prepared using the aforementioned technical solution. This mushroom fiber electrode exhibits excellent biocompatibility and can provide new methods for fabricating implantable electronic devices and smart wearable sensors.

[0079] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0080] I. Preparation Method

[0081] Example 1

[0082] This embodiment provides a method for preparing a mushroom fiber electrode, including the following steps:

[0083] S1. The dried and dehydrated mushroom raw materials were treated in a water bath for 6 h at a water bath temperature of 100℃, and then treated in an alkaline bath in a sodium hydroxide solution with a molar concentration of 2 mol / L for 8 h at an alkaline bath temperature of 110℃. After that, the raw materials were crushed, stirred, and centrifuged (10000 rpm, 20 min). The precipitate was then freeze-dried at -80℃ for 24 h to obtain alkaline-extracted mushroom samples.

[0084] S2, Weigh 0.5 g of the alkaline-extracted mushroom sample obtained in step S1, and dissolve it thoroughly in 7.12 ml of 1-ethyl-3-methylimidazolium acetate solution with a density of 1.1 g / ml under the conditions of 110℃ and 200 rpm to obtain a mushroom solution with a mass fraction of 6%.

[0085] S3, Add conductive functional material (PEDOT:PSS) to the mushroom solution obtained in step S2, stir and disperse to obtain mushroom composite spinning solution, as shown in the figure. Figure 1 As shown in the right figure.

[0086] In the mushroom composite spinning solution, the mass ratio of mushroom solution to conductive functional material is 1:1.

[0087] S4, the mushroom composite spinning solution obtained in step S3 is extruded from the spinneret using a metering pump into a coagulation bath (deionized water, 100℃, 45min) for solidification and stretching, with a coagulation stretching ratio of 200%. The initially formed conductive mushroom fiber filaments are then subjected to ion exchange and stretching four times in a displacement bath (deionized water, 100℃, 50min), with a displacement stretching ratio of 200%. The replaced conductive mushroom fiber filaments are then dehydrated, dried, and wound to obtain continuous and uniform conductive mushroom fiber filaments, as shown in the image below. Figure 2 As shown.

[0088] Comparative Example 1

[0089] Comparative Example 1 provides a method for preparing mushroom fiber. The main difference from Example 1 is that no conductive functional material is added. Otherwise, it is largely the same as the Example and will not be described again here.

[0090] Figure 1 The mushroom spinning solution in Comparative Example 1 (left figure) and the conductive mushroom spinning solution in Example 1 (right figure).

[0091] A photograph of the mushroom fiber prepared in Comparative Example 1 is shown below. Figure 2 As shown, the mushroom fibers are pale yellow, while the conductive mushroom fibers are black.

[0092] Figure 3 The images show the microstructures of the mushroom fibers prepared in Comparative Example 1 (left image) and the conductive mushroom fibers prepared in Example 1. As can be seen, the surface of the conductive mushroom fibers is cauliflower-like, indicating that the mushroom / PEDOT:PSS fibers were successfully prepared.

[0093] Figure 4 The infrared absorption spectra of the mushroom fiber prepared in Comparative Example 1 (see figure below) and the conductive mushroom fiber prepared in Example 1 show obvious characteristic peaks of PEDOT:PSS, such as at 1514 cm⁻¹. -1 The infrared absorption peaks correspond to C=C bond vibrations; 920, 1060 cm⁻¹ -1 The nearby absorption peaks correspond to the stretching vibrations of the C—O—C bond in the thiophene cycloethylene group, indicating that mushroom / PEDOT:PSS fibers were successfully prepared.

[0094] Figure 5 The X-ray diffraction patterns of the mushroom fiber prepared in Comparative Example 1 and the conductive mushroom fiber prepared in Example 1 show characteristic peaks of PEDOT:PSS at 19.3° and 26.2°, indicating that the mushroom / PEDOT:PSS fiber was successfully prepared.

[0095] The electrical properties of the conductive mushroom fibers prepared in Example 1 were tested, and the test results are as follows: Figure 6As shown, the resistance of 1mm conductive mushroom fiber is approximately 39MΩ, indicating that the fiber has conductive properties and is expected to be used in implantable electronic devices, smart wearable sensors, and other fields.

[0096] Examples 2-4 and Comparative Example 2

[0097] Examples 2-4 and Comparative Example 2 provide a method for preparing a mushroom fiber electrode. Compared with Example 1, the difference lies in the change of the mass ratio of mushroom solution to conductive functional material in step S3, as shown in the table below. The rest is roughly the same as in Example 1 and will not be repeated here.

[0098]

[0099] Experiments show that mushroom fiber electrodes can be successfully prepared in Examples 2-4.

[0100] Within the range of a mass ratio of mushroom solution to conductive functional material of 1:(0.05-20), the electrical properties of the prepared mushroom fiber electrode continuously improve as the content of conductive functional material increases, but the corresponding mechanical properties first increase and then decrease.

[0101] When the mass ratio of mushroom solution to conductive functional material is greater than 1:0.05, the electrical performance of the mushroom fiber electrode is poor due to the insufficient amount of conductive functional material.

[0102] When the mass ratio of mushroom solution to conductive functional material is less than 1:20 (Comparative Example 2), there is too much conductive functional material, making it difficult to disperse the spinning solution evenly, resulting in poor formability of conductive mushroom fibers and difficulty in spinning.

[0103] Examples 5-10 and Comparative Example 3

[0104] Examples 5-10 and Comparative Example 3 provide a method for preparing a mushroom fiber electrode. Compared with Example 1, the difference lies in the change of the conductive functional material used in step S3, as shown in the table below. The rest is largely the same as in Example 1 and will not be repeated here.

[0105]

[0106] Experiments show that mushroom fiber electrodes can be successfully prepared in Examples 5-11.

[0107] P-type conductive polymer PEDOT: PSS can be replaced with one or more of polypyrrole (PPy), polyaniline (PANI), poly(p-styrene) (PPV), poly(3-hexylthiophene) (P3HT), and poly[3-(4-carboxybutyl)thiophene-2,5-diyl] (P3CT).

[0108] The N-type conductive polymer can be replaced by one or more of the following: polybenzimidazole dibenzophenanthrene (BBL), polybenzodifurandione (PBFDO), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-stat-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione] (PDADF), and 6H-pyrrolo[3,2-b:4,5-b']bis[1,4]benzothiazine ladder polymer (PBBTL).

[0109] Conductive functional materials can also be one or more of the following: single-arm carbon nanotubes, multi-walled carbon nanotubes, graphite, graphene, graphene oxide, reduced graphene oxide, silver nanowires, two-dimensional metal nitrides and carbides (MXene), metal oxides, metal-organic frameworks (MOFs), conductive covalent organic frameworks (COFs), and quantum dots.

[0110] Two-dimensional metal nitrides and carbides MXene can be replaced with Ti2CT x Nb2CT x V2CT x TiVCT x Ti3CNT x V2NT x Nb4C3T, Mo 4 / 3 Y 2 / 3 CT x (Nb, Zn)4C3T x (TiV)2CT x One or more of them.

[0111] The metal oxide can be replaced by one or more of the following: tin oxide (SnO2), zinc oxide (ZnO), aluminum oxide (Al2O3), indium tin oxide (ITO), antimony-doped tin dioxide (ATO), and aluminum-doped zinc oxide (ZAO);

[0112] Metal-organic frameworks can be replaced by one or more of zirconium-based metal-organic frameworks, copper catecholate, copper-based metal-organic frameworks, cobalt-based metal-organic frameworks, hexaaminotriphenyl copper, and lanthanide metal-organic frameworks;

[0113] The conductive covalent organic framework can be replaced by one or more of the following: nitrogen- and sulfur-doped bis(thiazolyl) covalent organic framework, metal tetraphenylporphyrin-based covalent organic framework, 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic framework, and Janus diketone-based highly conductive conjugated covalent organic framework.

[0114] Quantum dots can be replaced by one or more of perovskite quantum dots, metal oxide quantum dots, or sulfide quantum dots.

[0115] Experiments show that the dispersant can also be other ionic liquids, such as tris(2-hydroxyethyl)methylammonium acetate, tris(2-hydroxyethyl)methylammonium methanesulfonate, tetrabutylammonium hydroxide, 1-butyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 2-bromo-1-allyl-3-methylimidazolium, 1-butyl-3-methylimidazolium bromide, and methyl 1-ethyl-3-methylimidazolium sulfate, all of which can be used to prepare mushroom fiber electrodes.

[0116] Dispersants can also be mixed solvents consisting of ionic liquids and co-solvents.

[0117] Specifically, the ionic liquid is one of tris(2-hydroxyethyl)methylammonium acetate or tris(2-hydroxyethyl)methylammonium methanesulfonate, and the co-solvent is ethylenediamine.

[0118] Alternatively, the ionic liquid is one of tetrabutylammonium hydroxide, 1-butyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1-ethyl-3-methylimidazolium chloride.

[0119] The cosolvent is one of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolinone, and hexamethylphosphoric triamine.

[0120] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method of preparing a mushroom fiber electrode, characterized by, The method comprises the following steps: S1, drying and dehydrating mushroom raw materials are treated by water bath and alkali bath, then crushed and stirred, centrifuged and precipitated, and the precipitate is dried to obtain an alkali-extracted mushroom sample; S2, the alkali-extracted mushroom sample obtained in step S1 is fully dissolved in a dispersing agent to obtain a mushroom solution with a mass fraction of 0.5%-35%; The dispersing agent is an ionic liquid or a mixed solvent composed of an ionic liquid and a cosolvent; The ionic liquid is one or more of tris(2-hydroxyethyl)methylammonium acetate, tris(2-hydroxyethyl)methylammonium methanesulfonate, tetrabutylammonium hydroxide, 1-butyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 2-bromo-1-allyl-3-methylimidazolium, 1-butyl-3-methylimidazolium bromide, and 1-ethyl-3-methylimidazolium methyl sulfate; The cosolvent is one or more of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, ethylenediamine, 1,3-dimethyl-2-imidazolidinone, and hexamethylphosphoric triamide; S3, an electrically conductive functional material is added to the mushroom solution obtained in step S2, and stirred and dispersed to obtain a mushroom composite spinning solution; wherein the mass ratio of the mushroom solution to the electrically conductive functional material is 1:(0.05-20); S4, the mushroom composite spinning solution obtained in step S3 is extruded from a spinneret into a coagulation bath to solidify and stretch to form a primary shape, and the primary shaped electrically conductive mushroom fiber filament is repeatedly introduced into a displacement bath for solvent displacement and further stretching; the electrically conductive mushroom fiber filament after displacement is heat set to remove moisture, dried and wound, thereby obtaining a continuous and uniform electrically conductive mushroom filament fiber with a diameter of 10-500 μm.

2. The method of claim 1, wherein the mushroom fiber electrode is prepared by the steps of: In step S2, the dispersing agent is a mixed solvent composed of an ionic liquid and a cosolvent; the ionic liquid is one of tris(2-hydroxyethyl)methylammonium acetate and tris(2-hydroxyethyl)methylammonium methanesulfonate, and the cosolvent is ethylenediamine; Alternatively, the ionic liquid is one of tetrabutylammonium hydroxide, 1-butyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1-ethyl-3-methylimidazolium chloride; and the cosolvent is one of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and hexamethylphosphoric triamide.

3. The method of claim 1, wherein the mushroom fiber electrode is prepared by the steps of: The electrically conductive functional material is one or more of a P-type conductive polymer, an N-type conductive polymer, a single-walled carbon nanotube, a multi-walled carbon nanotube, graphite, graphene, graphene oxide, reduced graphene oxide, silver nanowire, a two-dimensional metal nitride and carbide, a metal oxide, a metal-organic framework, a conductive covalent organic framework, and a quantum dot.

4. The method of claim 3, wherein the mushroom fiber electrode is prepared by the steps of: The P-type conductive polymer is one or more of polypyrrole, polyaniline, poly(p-phenylene styrene), PEDOT:PSS, poly(3-hexylthiophene), poly[3-(4-carboxybutyl)thiophene-2,5-diyl]; the N-type conductive polymer is one or more of poly(ether imide)-doped PEDOT:PSS, poly(benzimidazobenzophenanthroline), poly(benzodifuranedione), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-stat-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione], 6H-pyrrolo[3,2-b:4,5-b']bis[1,4]benzothiazine ladder polymer; the two-dimensional metal nitride and carbide MXene is one or more of Ti3C2T x , Ti2CT x , Nb2CT x , V2CT x , TiVCT x , Ti3CNT x , V2NT x , Nb4C3T, Mo 4 / 3 Y 2 / 3 CT x , (Nb, Zn)4C3T x , (TiV)2CT x .

5. The method of claim 3, wherein the mushroom fiber electrode is prepared by the steps of: The metal oxide is one or more of molybdenum oxide, tin oxide, zinc oxide, aluminum oxide, indium tin oxide, antimony-doped tin dioxide, aluminum-doped zinc oxide.

6. The method of claim 3, wherein the mushroom fiber electrode is prepared by the steps of: The metal organic framework is one or more of zirconium-based metal organic framework, hexaammine triphenyl nickel, catechol acid copper, copper-based metal organic framework, cobalt-based metal organic framework, hexaammine triphenyl copper, lanthanide metal organic framework.

7. The method of claim 3, wherein the mushroom fiber electrode is prepared by the steps of: The conductive covalent organic framework is one or more of nitrogen and sulfur-doped bithiazole-based covalent organic framework, metal tetraphenyl porphyrin-based covalent organic framework, nickel phthalocyanine-tetraazacycloalkene conjugated framework material, 2,4,6-trimethoxy-1,3,5-benzene tricarboxaldehyde-2,6-diamino anthraquinone covalent organic framework, Janus diketone-based high-conductivity conjugated covalent organic framework.

8. The method of claim 3, wherein the mushroom fiber electrode is prepared by the steps of: The quantum dot is one or more of carbon quantum dot, perovskite quantum dot, metal oxide or sulfide quantum dot.

9. The method of claim 1, wherein the mushroom fiber electrode is prepared by the steps of: In step S4, the shape of the jet orifice of the spinneret is circular, hollow, polygonal, multi-lobed, square, Y-shaped, double-crossed or flat.

10. The method of claim 1, wherein the mushroom fiber electrode is prepared by the steps of: In step S4, the coagulation bath is one or more of deionized water, alcohol, alkali solution, metal salt solution; the coagulation bath temperature is 20-150℃; the coagulation bath time is 15min-2h; the coagulation draft ratio is 10%-300%.

11. The method of claim 1, wherein the mushroom fiber electrode is prepared by the steps of: In step S4, the displacement bath is one or more of deionized water, alcohol, alkali solution, metal salt solution.

12. The method of claim 11, wherein the mushroom fiber electrode is prepared by the steps of: In step S4, the displacement bath temperature is 20-150℃; the displacement draft ratio is 10%-300%; the displacement bath time is 5min-2h.

13. The method of claim 1, wherein the mushroom fiber electrode is prepared by the steps of: In step S1, during the alkali bath treatment, the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and the molar concentration of the alkaline solution is 0.05-5mol / L.

14. A mushroom fiber electrode, characterized by, Prepared by the preparation method of any one of claims 1-13. Prepared by the preparation method of any one of claims 1-13.

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