Mushroom fiber electrode and preparation method thereof

Abstract

The invention 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, carrying out water bath and alkali bath treatment to obtain an alkali-extracted mushroom sample; fully dissolving the alkali-extracted mushroom sample in a selected dispersing agent to obtain a mushroom solution with the mass fraction of 0.5-35%, and adding a conductive functional material into the mushroom solution to obtain a mushroom composite spinning solution; extruding the mushroom composite spinning solution from a spinneret plate through a metering pump into a coagulating bath for curing, drafting and forming, then enabling the primarily formed conductive mushroom fiber filaments to enter a replacement bath for multiple times for solvent replacement, and further drafting; the replaced conductive mushroom fiber filaments are subjected to heat setting to remove moisture, and the continuous and uniform conductive mushroom filament fibers with the diameter being 10-500 microns are obtained. The prepared mushroom fiber electrode is good in stability, excellent in conductivity, low in contact resistance and good in tensile property, and has a good application prospect in the aspects of implantable electronic devices, intelligent wearable sensors and the like.

Description

Technical Field

[0001] The invention relates to the technical field of fiber-based electronic materials, and in particular to a mushroom fiber electrode and a preparation method thereof. Background Art

[0002] Conductive fibers have the advantages of good flexibility, light weight, strong textile properties and weavability, and have great application potential in the field of multifunctional electronic fabrics. Fiber electrodes are an important component of temperature, humidity, pressure, biochemical sensors, etc. in multifunctional electronic fabrics, and have a significant impact on the performance, manufacturing process and cost of the device.

[0003] my country's mushroom production ranks among the highest in the world. The chitin rich in its cell walls is the second largest renewable polymer in nature after cellulose. It has the advantages of biodegradability, biocompatibility, antibacterial and renewability. The fibers made after spinning retain their own excellent properties and have great potential in the field of textile materials.

[0004] The fiber made from mushrooms is low-cost, renewable, and has good biocompatibility. The development of mushroom fiber electrodes not only expands the application field of mushrooms, but also provides new ideas for the development of new flexible electrodes. However, the electrical insulation of mushroom fibers makes it difficult to be used directly. To solve this problem, the present invention provides a mushroom fiber electrode and a preparation method thereof. Summary of the invention

[0005] The present application provides a mushroom fiber electrode and a preparation method thereof, aiming to provide a method for making a fiber electrode using mushrooms as raw materials, and to provide a new idea for expanding conductive regenerated fibers.

[0006] The preparation method mixes the conductive functional material with mushrooms to prepare a spinning solution, and prepares a continuous, highly conductive, biocompatible conductive mushroom filament fiber electrode through wet spinning technology. The mushroom fiber electrode provided by the present invention has good stability, excellent conductivity, low contact impedance, good tensile performance, and has good application prospects in implantable electronic devices, smart wearable sensors, etc.

[0007] In a first aspect, an embodiment of the present application provides a method for preparing a mushroom fiber electrode, comprising the following steps:

[0008] S1, treating the dried and dehydrated mushroom raw material in a water bath and an alkali bath, then crushing, stirring, centrifuging and precipitating, and drying the precipitate to obtain an alkali-extracted mushroom sample;

[0009] S2, fully dissolving the alkali-extracted mushroom sample obtained in step S1 in a dispersant to obtain a mushroom solution with a mass fraction of 0.5% to 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 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-allyl-3-methylimidazolium bromide ([AMIM]Br), 1-butyl-3-methylimidazolium bromide ([BMIM]Br), and 1-ethyl-3-methylimidazolium methyl sulfate ([EMIM]Ms);

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

[0013] S3, adding a conductive functional material to the mushroom solution obtained in step S2, stirring and dispersing, to obtain a mushroom composite spinning solution;

[0014] S4, extruding the mushroom composite spinning solution obtained in step S3 from the spinneret into a coagulation bath through a metering pump for solidification and stretching, and then placing the initially formed conductive mushroom fiber filaments into a displacement bath for multiple times for solvent displacement and further stretching; heat-setting the replaced conductive mushroom fiber filaments to remove moisture, drying and rolling, so as to obtain continuous and uniform conductive mushroom filament fibers with a diameter of 10 to 500 μm.

[0015] Further, in step S2, the dispersant is a mixed solvent consisting of an ionic liquid and a co-solvent; the ionic liquid is tris(2-hydroxyethyl)methylammonium acetate ([THEMA][OAc]), tris(2-hydroxyethyl)methylammonium methanesulfonate ([THEMA][MeSO 3 ]) wherein 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 bonding of chitin in the mushroom fiber, and is beneficial to the dissolution of the mushroom fiber.

[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); and the co-solvent is one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), and hexamethylphosphoric triamide (HMPA).

[0017] Further, in step S3, the mass ratio of the mushroom solution to the conductive functional material is 1:

[0018] (0.05-20).

[0019] Further, the conductive functional material is one or more of 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 nitride and carbide (MXene), metal oxide, metal organic framework (MOF), conductive covalent organic framework (COF), quantum dot;

[0020] Further, the P-type conductive polymer is one or more of polypyrrole, polyaniline, poly(p-phenylene glycol), PEDOT:PSS, poly(3-hexylthiophene), and poly[3-(4-carboxybutyl)thiophene-2,5-diyl];

[0021] The N-type conductive polymer is one or more of polyetherimide (PEI) doped PEDOT:PSS, polybenzimidazole dibenzophenanthroline (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;

[0022] The two-dimensional metal nitride and carbide MXene is Ti 3 C 2 T x 、Ti 2 CT x , Nb 2CT x 、V 2 CT x 、TiVCT x 、Ti 3 CNT x 、V 2 NT x , Nb 4 C 3 T.Mo 4 / 3 Y 2 / 3 CT x 、(Nb,Zn) 4 C 3 T x 、(TiV) 2 CT x One or more of;

[0023] Furthermore, the metal oxide is molybdenum oxide (MoO 2 ), tin oxide (SnO 2 )、ZnO、Al2O3 2 O 3 ), aluminum oxide (Al 2 O 3 ), indium tin oxide (ITO), antimony-doped tin dioxide (ATO), aluminum-doped zinc oxide (ZAO) or one or more thereof;

[0024] Further, the metal organic framework is one or more of a zirconium-based metal organic framework, hexamidotriphenylene nickel, catechol copper, a copper-based metal organic framework, a cobalt-based metal organic framework, hexamidotriphenylene copper, and a lanthanide metal organic framework;

[0025] Further, the conductive covalent organic framework is one or more of nitrogen- and sulfur-doped bisthiazolyl covalent organic framework, metal tetraphenylporphyrin-based covalent organic framework, nickel phthalocyanine-tetraazacyclopentene conjugated framework material, 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic framework, and Janus diketone-based high-conductivity conjugated covalent organic framework;

[0026] Furthermore, the quantum dots are one or more of carbon quantum dots, perovskite quantum dots, metal oxide or sulfide quantum dots.

[0027] Furthermore, in step S4, the spinneret of the spinneret is circular, hollow or shaped; the shaped is triangular, trilobal, polygonal, multilobal, square, pentagonal, Y-shaped double cross or flat. In this way, the cross section of the prepared fiber can be of different shapes.

[0028] 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°C to 150°C; the coagulation bath time is 15min to 2h; and the coagulation draft ratio is 10% to 300%.

[0029] Furthermore, in step S4, the displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.

[0030] Furthermore, in step S4, the displacement bath temperature is 20°C to 150°C; the displacement draft ratio is 10% to 300%; and the displacement bath time is 5 min to 2 h.

[0031] Furthermore, in step S4, the number of replacements is 2 to 5 times.

[0032] 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 to 5 mol / L.

[0033] In a second aspect, an embodiment of the present application provides a mushroom fiber electrode, which is prepared by any of the aforementioned technical solutions.

[0034] The mushroom fiber electrode has good stability, excellent conductivity, low contact impedance, and good tensile properties, and has good application prospects in implantable electronic devices, smart wearable sensors, etc.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The preparation method of the mushroom fiber electrode provided in the present application first removes the soluble polysaccharides and glycoproteins in the mushrooms through water bath pretreatment and alkaline bath pretreatment, and then freeze-dries the mushroom raw materials at -20 to -80°C or dry-dries them at 40 to 100°C to obtain an alkali-extracted mushroom sample. 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 to the mushroom solution to obtain a mushroom composite spinning solution; the mushroom composite spinning solution is extruded from the spinneret into a coagulation bath through a metering pump for curing and stretching, and then the initially formed conductive mushroom fiber filaments are repeatedly placed in a displacement bath for solvent displacement and further stretching; the replaced conductive mushroom fiber filaments are heat-set to remove moisture to obtain continuous and uniform conductive mushroom filament fibers with a diameter of 10 to 500 μm.

[0037] (2) The present application uses mushrooms as raw materials to prepare fiber electrodes. The raw materials are widely available, inexpensive, renewable, energy-saving and have good biocompatibility.

[0038] (3) The mushroom fiber electrode prepared by the present invention has excellent biocompatibility and can provide a new method for preparing implantable electronic devices and smart wearable sensors.

[0039] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0041] Figure 1 These are actual pictures of the mushroom fiber spinning solution and the mushroom / PEDOT:PSS composite spinning solution in Example 1.

[0042] Figure 2 The actual pictures are of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1.

[0043] Figure 3 The microscopic morphology of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1.

[0044] Figure 4 The infrared spectra of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1.

[0045] Figure 5 X-ray diffraction patterns of the conductive mushroom fiber prepared in Example 1 and the mushroom fiber prepared in Comparative Example 1.

[0046] Figure 6 The electrical properties (resistance) of the mushroom fiber electrode prepared in Example 1. DETAILED DESCRIPTION

[0047] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0049] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0050] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0051] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0052] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0053] In the description of the embodiments of the present application, unless otherwise clearly specified and limited, technical terms such as "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the internal connection of two elements or the interaction relationship between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the embodiments of the present application can be understood according to the specific circumstances.

[0054] In the prior art, there is no disclosed method for preparing mushroom fiber electrodes.

[0055] The present invention provides a method for preparing a mushroom fiber electrode, comprising the following steps:

[0056] S1, treating the dried and dehydrated mushroom raw material in a water bath for 0.3-6 hours and then in an alkali bath for 0.5-8 hours to remove soluble polysaccharides and glycoproteins in the mushroom, then crushing, stirring, centrifuging and precipitating, freeze-drying the precipitate at -20 to -80°C or drying at 40 to 100°C for 24 to 48 hours to obtain an alkali-extracted mushroom sample;

[0057] The water bath temperature is 40°C to 100°C and the alkali bath temperature is 25°C to 100°C.

[0058] During centrifugal sedimentation, the centrifugal speed is 5000rpm to 20000rpm, and the centrifugal time is 5min to 35min.

[0059] During the alkaline bath treatment, the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate.

[0060] The molar concentration of the alkaline solution is 0.05 to 5 mol / L.

[0061] S2, fully dissolving the alkali-extracted mushroom sample obtained in step S1 in a dispersant at a temperature of 85° C. to 130° C. and a rotation speed of 100 rpm to 2000 rpm to obtain a mushroom solution with a mass fraction of 0.5% to 35%;

[0062] The dispersant is an ionic liquid, or a mixed solvent consisting of an ionic liquid and a co-solvent.

[0063] 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-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 2-allyl-3-methylimidazolium bromide ([AMIM]Br), 1-butyl-3-methylimidazolium bromide ([BMIM]Br), and 1-ethyl-3-methylimidazolium methyl sulfate ([EMIM]Ms).

[0064] When the dispersant is a mixed solvent consisting of an ionic liquid and a co-solvent, the ionic liquid is tris(2-hydroxyethyl)methylammonium acetate ([THEMA][OAc]), tris(2-hydroxyethyl)methylammonium methanesulfonate ([THEMA][MeSO 3]) and the co-solvent is ethylenediamine. By adding ionic liquid to ethylenediamine (EDA), the additional EDA enhances the hydrogen bonding ability of the IL / EDA mixture, weakens the interchain hydrogen bonding of chitin in mushroom fiber, and is beneficial to the dissolution of mushroom fiber.

[0065] 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-imidazolidinone (DMI), and hexamethylphosphoric triamide (HMPA).

[0066] S3, adding conductive functional material to the mushroom solution obtained in step S2, stirring and dispersing, to obtain a mushroom composite spinning solution.

[0067] Among them, the mass ratio of the mushroom solution to the conductive functional material is 1:(0.05-20).

[0068] The conductive functional material is one or more of 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 nitride and carbide (MXene), metal oxide, metal organic framework (MOF), conductive covalent organic framework (COF), and quantum dots.

[0069] Further, the P-type conductive polymer is one or more of polypyrrole, polyaniline, poly(p-phenylene glycol), 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 dibenzophenanthroline (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; the two-dimensional metal nitride and carbide MXene is Ti3 C 2 T x 、Ti 2 CT x , Nb 2 CT x 、V 2 CT x 、TiVCT x 、Ti 3 CNT x 、V 2 NT x , Nb 4 C 3 T.Mo 4 / 3 Y 2 / 3 CT x 、(Nb,Zn) 4 C 3 T x 、(TiV) 2 CT x One or more of;

[0070] Furthermore, the metal oxide is molybdenum oxide (MoO 2 ), tin oxide (SnO 2 )、ZnO、Al2O3 2 O 3 ), aluminum oxide (Al 2 O 3 ), indium tin oxide (ITO), antimony-doped tin dioxide (ATO), aluminum-doped zinc oxide (ZAO) or one or more thereof;

[0071] Further, the metal organic framework is one or more of a zirconium-based metal organic framework, hexamidotriphenylene nickel, catechol copper, a copper-based metal organic framework, a cobalt-based metal organic framework, hexamidotriphenylene copper, and a lanthanide metal organic framework;

[0072] Furthermore, the conductive covalent organic framework is one or more of a nitrogen- and sulfur-doped disthiazolyl covalent organic framework, a metal tetraphenylporphyrin-based covalent organic framework, a nickel phthalocyanine-tetraazacyclopentene conjugated framework material, a 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic framework, and a Janus dione-based high-conductivity conjugated covalent organic framework.

[0073] S4, extruding the mushroom composite spinning solution obtained in step S3 from the spinneret into a coagulation bath through a metering pump for solidification and stretching, and then placing the initially formed conductive mushroom fiber filaments into a displacement bath for multiple times for solvent displacement and further stretching; heat-setting the replaced conductive mushroom fiber filaments to remove moisture, drying and rolling, so as to obtain continuous and uniform conductive mushroom filament fibers with a diameter of 10 to 500 μm.

[0074] The coagulation bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.

[0075] The coagulation bath temperature is 20°C to 150°C; the coagulation bath time is 15min to 2h; and the coagulation draft ratio is 10% to 300%.

[0076] The displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.

[0077] The displacement bath temperature is 20°C to 150°C; the displacement draft ratio is 10% to 300%; the displacement bath time is 5min to 2h; and the number of displacements is 2 to 5 times.

[0078] The spinneret of the spinneret is in the shape of a circle, a hollow or a special shape (triangle, trilobal, polygonal, multilobal, square, pentagonal, Y-shaped double cross, flat).

[0079] In the second aspect, the embodiment of the present application provides a mushroom fiber electrode, which is prepared by the above technical solution. The mushroom fiber electrode has excellent biocompatibility and can be used to develop a new method for preparing implantable electronic devices and smart wearable sensors.

[0080] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be obtained commercially.

[0081] 1. Preparation method

[0082] Example 1

[0083] This embodiment provides a method for preparing a mushroom fiber electrode, comprising the following steps:

[0084] S1, treating the dried and dehydrated mushroom raw material in a water bath for 6 hours at a water bath temperature of 100° C., then treating it in an alkaline bath in a sodium hydroxide solution with a molar concentration of 2 mol / L for 8 hours at a temperature of 110° C., then crushing, stirring, centrifuging (10000 rpm, 20 min), and freeze-drying the precipitate at -80° C. for 24 hours to obtain an alkali-extracted mushroom sample;

[0085] S2, weighing 0.5 g of the alkali-extracted mushroom sample obtained in step S1, fully stirring and dissolving it in 7.12 ml of 1-ethyl-3-methylimidazolium acetate solution with a density of 1.1 g / ml at a temperature of 110° C. and a rotation speed of 200 rpm, to obtain a mushroom solution with a mass fraction of 6%;

[0086] S3, adding conductive functional material (PEDOT:PSS) to the mushroom solution obtained in step S2, stirring and dispersing, to obtain a mushroom composite spinning solution, the actual picture of which is as follows Figure 1 As shown in the right figure.

[0087] In the mushroom composite spinning solution, the mass ratio of the mushroom solution to the conductive functional material is 1:1.

[0088] S4, the mushroom composite spinning solution obtained in step S3 is extruded from the spinneret through a metering pump into a coagulation bath (deionized water, 100°C, 45min) for curing and stretching, and the coagulation and stretching multiple is 200%. Then, the initially formed conductive mushroom fiber filaments are placed in a displacement bath (deionized water, 100°C, 50min) for ion exchange and stretching 4 times, and the displacement and stretching multiple is 200%. The conductive mushroom fiber filaments after displacement are dehydrated, dried and rolled up to obtain continuous and uniform conductive mushroom filament fibers, as shown in the actual figure. Figure 2 shown.

[0089] Comparative Example 1

[0090] Comparative Example 1 provides a method for preparing mushroom fiber. Compared with Example 1, the main difference is that no conductive functional material is added, and the rest is generally the same as the example, which will not be repeated here.

[0091] Figure 1 The mushroom spinning solution in Comparative Example 1 (left picture) and the conductive mushroom spinning solution in Example 1 (right picture).

[0092] The actual picture of mushroom fiber prepared in Comparative Example 1 is as follows Figure 2 As shown, it can be seen that the mushroom fibers are light yellow and the conductive mushroom fibers are black.

[0093] Figure 3 The microscopic morphology of the mushroom fiber prepared in comparative example 1 (left picture) and the conductive mushroom fiber prepared in example 1. It can be seen that the surface of the conductive mushroom fiber is cauliflower-shaped, indicating that the mushroom / PEDOT:PSS fiber was successfully prepared.

[0094] Figure 4 The infrared absorption spectra of the mushroom fiber prepared in comparative example 1 (below) and the conductive mushroom fiber prepared in example 1 show obvious characteristic peaks of PEDOT:PSS, such as at 1514 cm -1The infrared absorption peaks correspond to the vibration of C=C bond; 920, 1060cm -1 The nearby absorption peaks correspond to the stretching vibration of the C—O—C bond of the ethylene group of the thiophene ring, indicating that the mushroom / PEDOT:PSS fibers were successfully prepared.

[0095] Figure 5 The X-ray diffraction diagrams 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.

[0096] The electrical properties of the conductive mushroom fiber prepared in Example 1 were tested, and the test results are as follows: Figure 6 As shown in the figure, it can be seen that the resistance of 1mm conductive mushroom fiber is about 39MΩ, indicating that the fiber has conductive properties and is expected to be used in implantable electronic devices, smart wearable sensors and other fields.

[0097] Examples 2-4 and Comparative Example 2

[0098] Embodiments 2-4 and comparative example 2 provide a method for preparing a mushroom fiber electrode, which is different from embodiment 1 in that the mass ratio of the mushroom solution to the conductive functional material in step S3 is changed, as shown in the following table. The rest is roughly the same as embodiment 1 and will not be repeated here.

[0099]

[0100] Experiments show that Examples 2-4 can all successfully prepare mushroom fiber electrodes.

[0101] In the range of the mass ratio of mushroom solution to conductive functional material of 1:(0.05-20), as the content of conductive functional material continues to increase, the electrical properties of the prepared mushroom fiber electrode continue to improve, but the corresponding mechanical properties first increase and then decrease.

[0102] When the mass ratio of mushroom solution to conductive functional material is greater than 1:0.05, the electrical properties of the obtained mushroom fiber electrode are poor due to the small amount of conductive functional material.

[0103] When the mass ratio of the mushroom solution to the conductive functional material is less than 1:20 (Comparative Example 2), there is too much conductive functional material, the spinning solution is difficult to disperse evenly, the conductive mushroom fiber has poor formability, and is difficult to spin.

[0104] Examples 5-10 and Comparative Example 3

[0105] Examples 5-10 and Comparative Example 3 provide a method for preparing a mushroom fiber electrode. Compared with Example 1, the difference is that the conductive functional material used in step S3 is changed, as shown in the following table.

[0106] The rest is roughly the same as that of Example 1 and will not be described again.

[0107]

[0108] Experiments show that Examples 5-11 can all successfully prepare mushroom fiber electrodes.

[0109] P-type conductive polymer PEDOT: PSS can be replaced by one or more of polypyrrole (PPy), polyaniline (PANI), poly(p-phenylene vinylene) (PPV), poly(3-hexylthiophene) (P3HT), and poly[3-(4-carboxybutyl)thiophene-2,5-diyl] (P3CT).

[0110] The N-type conductive polymer can be replaced by one or more of polybenzimidazole dibenzophenanthroline (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).

[0111] The conductive functional material can also be one or more of 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.

[0112] Two-dimensional metal nitrides and carbides MXene can be replaced by Ti 2 CT x , Nb 2 CT x 、V 2 CT x 、TiVCT x 、Ti 3 CNT x 、V 2 NT x , Nb 4 C 3 T.Mo 4 / 3 Y 2 / 3 CT x 、(Nb,Zn) 4 C3 T x 、(TiV) 2 CT x One or more of .

[0113] Metal oxides can be replaced by tin oxide (SnO 2 )、ZnO、Al2O3 2 O 3 ), aluminum oxide (Al 2 O 3 ), indium tin oxide (ITO), antimony-doped tin dioxide (ATO), aluminum-doped zinc oxide (ZAO) or one or more thereof;

[0114] The metal organic framework can be replaced by one or more of a zirconium-based metal organic framework, copper catecholate, a copper-based metal organic framework, a cobalt-based metal organic framework, hexaaminotriphenylene copper, and a lanthanide metal organic framework;

[0115] The conductive covalent organic framework can be replaced by one or more of nitrogen- and sulfur-doped bithiazolyl-based covalent organic frameworks, metal tetraphenylporphyrin-based covalent organic frameworks, 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic frameworks, and Janus dione-based highly conductive conjugated covalent organic frameworks.

[0116] The quantum dots can be replaced by one or more of perovskite quantum dots, metal oxide or sulfide quantum dots.

[0117] Experiments show that the dispersant can also be other ionic liquids, such as the use of one or more of tris(2-hydroxyethyl)methylammonium acetate, tris(2-hydroxyethyl)methylammonium methanesulfonate, tetrabutylammonium hydroxide, 1-butyl-3-methylimidazole acetate, 1,3-dibutylimidazole acetate, 1,3-dimethylimidazole acetate, 1-ethyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole chloride, 2-allyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole bromide, and 1-ethyl-3-methylimidazole methyl sulfate, all of which can achieve the preparation of mushroom fiber electrodes.

[0118] The dispersant may also be a mixed solvent consisting of an ionic liquid and a co-solvent.

[0119] Specifically, the ionic liquid is one of tris(2-hydroxyethyl)methylammonium acetate and tris(2-hydroxyethyl)methylammonium methanesulfonate, and the co-solvent is ethylenediamine.

[0120] Alternatively, the ionic liquid is one of 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, and 1-ethyl-3-methylimidazolium chloride.

[0121] The co-solvent is one of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone and hexamethylphosphoric triamide.

[0122] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A method for preparing a mushroom fiber electrode, characterized in that: The following steps are involved: S1, treating the dried and dehydrated mushroom raw material in a water bath and an alkali bath, then crushing, stirring, centrifuging and precipitating, and drying the precipitate to obtain an alkali-extracted mushroom sample; S2, fully dissolving the alkali-extracted mushroom sample obtained in step S1 in a dispersant to obtain a mushroom solution with a mass fraction of 0.5% to 35%; The dispersant is an ionic liquid, or a mixed solvent consisting of an ionic liquid and a co-solvent; The ionic liquid is one or more of tris(2-hydroxyethyl)methylammonium acetate, tris(2-hydroxyethyl)methylammonium methanesulfonate, tetrabutylammonium hydroxide, 1-butyl-3-methylimidazole acetate, 1,3-dibutylimidazole acetate, 1,3-dimethylimidazole acetate, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole chloride, 2-allyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole bromide, and 1-ethyl-3-methylimidazole methyl sulfate; The co-solvent is one or more of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, ethylenediamine, 1,3-dimethyl-2-imidazolidinone, and hexamethylphosphoric triamide; S3, adding a conductive functional material to the mushroom solution obtained in step S2, stirring and dispersing, to obtain a mushroom composite spinning solution; S4, extruding the mushroom composite spinning solution obtained in step S3 from the spinneret into a coagulation bath through a metering pump for solidification and stretching, and then placing the initially formed conductive mushroom fiber filaments into a displacement bath for multiple times for solvent displacement and further stretching; heat-setting the replaced conductive mushroom fiber filaments to remove moisture, drying and rolling, so as to obtain continuous and uniform conductive mushroom filament fibers with a diameter of 10 to 500 μm.

2. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: 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 and tris(2-hydroxyethyl)methylammonium methanesulfonate, and the co-solvent 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-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1-ethyl-3-methylimidazolium chloride; the co-solvent is one of dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and hexamethylphosphoric triamide.

3. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: In step S3, the mass ratio of the mushroom solution to the conductive functional material is 1:(0.05-20).

4. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: The conductive functional material is one or more of 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 nitride and carbide, metal oxide, metal organic framework, conductive covalent organic framework, and quantum dot; Furthermore, the P-type conductive polymer is one or more of polypyrrole, polyaniline, poly(p-phenylene glycol), 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-doped PEDOT:PSS, polybenzimidazole dibenzophenanthroline, 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; the two-dimensional metal nitride and carbide MXene is 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 One or more of; Further, the metal oxide is one or more of molybdenum oxide, tin oxide, zinc oxide, aluminum oxide, aluminum oxide, indium tin oxide, antimony-doped tin dioxide, and aluminum-doped zinc oxide; Further, the metal organic framework is one or more of a zirconium-based metal organic framework, hexamidotriphenylene nickel, catechol copper, a copper-based metal organic framework, a cobalt-based metal organic framework, hexamidotriphenylene copper, and a lanthanide metal organic framework; Further, the conductive covalent organic framework is one or more of nitrogen- and sulfur-doped bisthiazolyl covalent organic framework, metal tetraphenylporphyrin-based covalent organic framework, nickel phthalocyanine-tetraazacyclopentene conjugated framework material, 2,4,6-trimethoxy-1,3,5-benzenetricarboxaldehyde-2,6-diaminoanthraquinone covalent organic framework, and Janus diketone-based high-conductivity conjugated covalent organic framework; Furthermore, the quantum dots are one or more of carbon quantum dots, perovskite quantum dots, metal oxide or sulfide quantum dots.

5. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: In step S4, the spinneret of the spinneret is in the shape of a circle, a hollow, a triangle, a trilobal, a polygon, a multilobal, a square, a pentagon, a Y-shaped double cross or a flat shape.

6. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: 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°C to 150°C; the coagulation bath time is 15min to 2h; and the coagulation draft multiple is 10% to 300%.

7. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: In step S4, the displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.

8. The method for preparing mushroom fiber electrodes according to claim 7, characterized in that: In step S4, the displacement bath temperature is 20°C to 150°C; the displacement draft ratio is 10% to 300%; and the displacement bath time is 5 minutes to 2 hours.

9. The method for preparing mushroom fiber electrodes according to claim 1, characterized in that: 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.

10. A mushroom fiber electrode, characterized in that: The method is prepared according to any one of claims 1 to 9.

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