Highly sensitive MXene-based sensing fiber and its preparation method and application

Abstract

The present application discloses a highly sensitive MXene-based sensing fiber, its preparation method and application, and belongs to the field of wearable sensing technology. The preparation method of the highly sensitive MXene-based sensing fiber of the present application includes: preparing a wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber, and twisting at least two strands of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers into a structural fiber bundle, and then composite sensing response coating on the surface of the structural fiber bundle to obtain a highly sensitive MXene-based sensing fiber. The preparation method of the present application can not only enhance the flexibility and mechanical stability of the MXene-based sensing fiber, so that it has good weavability and service life, but also enhance the sensing of the MXene-based sensing fiber to the environment and human physiological signals, so that the MXene-based sensing fiber has excellent response sensitivity, effectively improving the user experience.

Description

Technical Field

[0001] The present application belongs to the field of wearable sensor technology, and in particular to highly sensitive MXene-based sensor fibers, preparation methods, and applications thereof. Background Art

[0002] Wearable electronic sensor fabrics are smart textiles that integrate sensors, processors, and memory. They can monitor the physiological signals of the human body in real time and provide people with feedback on their physical condition. Among them, sensor fibers are key devices for collecting information about the human body and the environment. Their sensitivity, response time, and service life greatly affect the user experience. Therefore, the preparation of sensor fibers with high sensitivity, high mechanical toughness, and high structural stability has attracted much attention.

[0003] The prior art with patent number CN109239152B discloses an electrochemical sensing fabric, which is woven and integrated with multiple electrochemical fiber sensors and silver-silver chloride fiber reference electrodes, thereby realizing the simultaneous detection of different chemical components in sweat such as glucose, pH value and human electrolyte ions, and has broad prospects for use in the field of wearable electronics.

[0004] However, the electrochemical sensing fabrics described above have the following defects in practical applications: First, due to the constraints of high stiffness and low toughness of carbon-based fibers, the electrochemical sensing fibers are easily damaged and broken when subjected to force and deformation, and their actual service life is not ideal; second, the surface of carbon-based fibers is relatively smooth and has a small specific surface area, which is not conducive to the adhesion and dispersion of the sensing response coating, resulting in the sensitivity of the electrochemical sensing fibers needs to be improved. Summary of the invention

[0005] The present application solves the technical problems of poor flexibility and unsatisfactory sensitivity of existing multifunctional sensing fabrics by disclosing a highly sensitive MXene-based sensing fiber and its preparation method and application.

[0006] To achieve the above objectives, the first aspect of the present application provides a method for preparing a highly sensitive MXene-based sensing fiber, the preparation method comprising:

[0007] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0008] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0009] A composite sensing response coating is applied to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a highly sensitive MXene-based sensing fiber.

[0010] In some embodiments, the method for preparing the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber comprises:

[0011] Wet spinning a mixed dispersion containing titanium carbide, (PEDOT:PSS) and polyrotaxane to obtain primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fibers;

[0012] The primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fiber is subjected to chemical crosslinking, electrostatic coupling, hot pressing and vacuum drying in sequence to obtain wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers.

[0013] In some embodiments, the sensed responsive coating includes a pressure responsive coating, a temperature responsive coating, an ion responsive coating, a glucose responsive coating, and a pH responsive coating.

[0014] In some embodiments, the pressure responsive coating is formed by a dielectric polymer;

[0015] The dielectric polymer includes at least one of polyurethane, polydimethylsiloxane, polyvinylidene fluoride, and polyimide;

[0016] In some embodiments, the temperature responsive coating is formed by a thermoresponsive polymer;

[0017] The thermoresponsive polymer comprises at least one of polyethylene oxides of different molecular weights or mixtures thereof, polyethylene glycol methacrylate, polyethylene glycol acrylate, poly(N-isopropylacrylamide), and paraffin;

[0018] In some embodiments, the ion-responsive coating sequentially comprises a (PEDOT:PSS) conductive layer and an ion-selective membrane composited on the (PEDOT:PSS) conductive layer;

[0019] The ion selective membrane precursor is a mixture of sodium tetraphenylborate, polyvinyl chloride, dioctyl sebacate and ion carrier;

[0020] In some embodiments, the glucose responsive coating sequentially comprises a zinc oxide nanorod coating and a metal nanoparticle or transition metal oxide coating composited on the zinc oxide nanorod coating;

[0021] The metal nanoparticles are at least one of Cu, Pt, Au, Ag, Ni, and Pd; the transition metal oxides are CuO, NiO, Cu 2 O, Fe 3 O 4 At least one of;

[0022] In some embodiments, the pH responsive coating is formed by a conductive polymer;

[0023] The conductive polymer includes at least one of polyaniline, poly(2,5)-dimethylaniline and poly(4,4)-benzidine.

[0024] Based on the preparation method described in the first aspect, the second aspect of the present application specifically provides a preparation method of a highly sensitive MXene-based pressure sensing fiber, the preparation method comprising the following steps:

[0025] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0026] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0027] After preparing a dielectric polymer into a dielectric polymer solution with a mass concentration of 6 to 60%, the dielectric polymer solution is uniformly coated on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a MXene-based structure fiber bundle with a surface composite dielectric layer;

[0028] At least two strands of the MXene-based structural fiber bundles with the surface composite dielectric layer are twisted to obtain a highly sensitive MXene-based pressure sensing fiber.

[0029] Based on the preparation method described in the first aspect, the third aspect of the present application specifically provides a method for preparing a highly sensitive MXene-based temperature sensing fiber, the preparation method comprising the following steps:

[0030] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0031] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0032] The titanium carbide / PEDOT / polyrotaxane structure fiber bundle is immersed in a thermal responsive polymer solution for 0.5 to 10 minutes, taken out and naturally dried, and the operation is repeated 1 to 8 times to obtain a highly sensitive MXene-based temperature sensing fiber.

[0033] Based on the preparation method described in the first aspect, the fourth aspect of the present application specifically provides a method for preparing a highly sensitive MXene-based ion sensing fiber, the preparation method comprising:

[0034] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0035] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0036] The surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle is uniformly coated with a (PEDOT:PSS) conductive layer to obtain a MXene-based structure fiber bundle with a surface composite conductive layer;

[0037] After preparing an ion selective membrane precursor solution containing sodium tetraphenylborate, polyvinyl chloride, dioctyl sebacate and ion carrier, the ion selective membrane precursor solution is drip-coated on the surface of the MXene-based structural fiber bundle of the surface composite conductive layer, and dried naturally to obtain a highly sensitive MXene-based ion sensing fiber.

[0038] Based on the preparation method described in the first aspect, the fifth aspect of the present application specifically provides a method for preparing a highly sensitive MXene-based pH sensing fiber, the preparation method comprising the following steps:

[0039] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0040] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0041] In a three-electrode system, cyclic voltammetry was used to deposit a conductive polymer on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a highly sensitive MXene-based pH sensing fiber.

[0042] Based on the preparation method described in the first aspect, the sixth aspect of the present application specifically provides a preparation method of a highly sensitive MXene-based glucose sensing fiber, the preparation method comprising the following steps:

[0043] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0044] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0045] In a three-electrode system, zinc oxide nanorods are deposited on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle by using a chronoamperometry method to obtain a MXene-based structure fiber bundle with a zinc oxide nanorod coating deposited on the surface;

[0046] The metal nanoparticles and / or transition metal oxide coating are deposited on the surface of the MXene-based structural fiber bundle on which the zinc oxide nanorod coating is deposited by using the chronoamperometry to obtain a high-sensitivity MXene-based glucose sensing fiber.

[0047] The seventh aspect of the present application also provides the application of the high-sensitivity MXene-based pressure sensing fiber, the high-sensitivity MXene-based temperature sensing fiber, the high-sensitivity MXene-based ion sensing fiber, the high-sensitivity MXene-based pH sensing fiber or the high-sensitivity MXene-based glucose sensing fiber of the present application for the preparation of multifunctional sensing integrated flexible fabrics.

[0048] Compared with the prior art, the advantages or beneficial effects of the embodiments of the present application include at least:

[0049] The preparation method provided in the first aspect of the present application can prepare a highly sensitive MXene-based sensing fiber by twisting at least two strands of wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments to form a wrinkled entangled structure fiber bundle and then composite the sensor response coating. On the one hand, the wrinkled entangled fiber bundle structure formed by twisting can provide more charge transfer channels, a larger specific surface area and contact area, which is beneficial to improve the conductivity and the adhesion amount of the sensor response coating material, thereby significantly enhancing the sensing of the environment and human physiological signals, making the MXene-based sensing fiber have higher sensitivity and shorter response time; on the other hand, the dynamic pulley effect produced by the adjustable porous structure, titanium carbide / PEDOT rigid interface structure and titanium carbide / polyrotaxane dynamic pulley interface structure in the titanium carbide / PEDOT / polyrotaxane composite fiber structure can synergize with the wrinkled entanglement structure of the twisted fiber bundle, effectively enhancing the flexibility and tensile strength of the titanium carbide / PEDOT / polyrotaxane sensing fiber, making it easy to weave and have good tolerance to mechanical deformation, effectively increasing the service life of the titanium carbide / PEDOT / polyrotaxane sensing fiber, and significantly improving the user experience. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments recorded in the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0051] Figure 1 This is a plane electron microscope scanning image of the titanium carbide / PEDOT / polyrotaxane composite fiber provided in the embodiment of the present application;

[0052] Figure 2 This is an electron microscope image of the twisted three-strand wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber provided in the embodiment of the present application;

[0053] Figure 3 The capacitance change rate of the highly sensitive MXene-based pressure sensing fiber (PSF-PU) under different pressures provided in the embodiments of the present application;

[0054] Figure 4 The resistance change rate of the highly sensitive MXene-based temperature sensing fiber (TSF-PEO) at different temperatures provided in the embodiments of the present application;

[0055] Figure 5 The voltage response results of the highly sensitive MXene-based pH sensing fiber (pH-SF-A) provided in the embodiments of the present application in different pH solutions;

[0056] Figure 6 The highly sensitive MXene-based ion sensing fiber (SF-Na + ) Voltage response test results in solutions with different sodium ion concentrations;

[0057] Figure 7 The highly sensitive MXene-based ion sensing fiber (SF-Ca) provided in the embodiment of the present application 2+ ) Voltage response test results in solutions with different calcium ion concentrations;

[0058] Figure 8 This is the current response of the highly sensitive MXene-based glucose sensor fiber (SF-Glu-Cu) provided in the embodiments of the present application in glucose solutions of different concentrations. DETAILED DESCRIPTION

[0059] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0060] In the following description of this embodiment, the term "and / or" is used to describe the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, B exists alone, and A and B exist at the same time. A and B can be singular or plural. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.

[0061] In the following description of this embodiment, the term "at least one" refers to one or more, and "plurality" refers to two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c", can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0062] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0063] Those skilled in the art should understand that in the following description of the embodiments of the present application, the order of serial numbers does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0064] Those skilled in the art will appreciate that the numerical ranges in the embodiments of the present application are to be understood as each intermediate value between the upper and lower limits of the scope also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded in the scope.

[0065] Unless otherwise specified, the technical / scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this application belongs. Although this application only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of this application. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0066] In a first aspect, the present application provides a method for preparing a highly sensitive MXene-based sensing fiber, and the preparation method preferably includes:

[0067] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0068] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0069] A composite sensing response coating is applied to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a highly sensitive MXene-based sensing fiber.

[0070] It should be noted that the specific number of strands, number of twisting turns and twisting operation method of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber are not particularly limited in the present embodiment, and can be completed in a twisting device according to a known fiber twisting method. For example, the number of twisting turns can be 5 to 30 turns; the number of strands of the composite fiber used for twisting can be 2 to 20 strands.

[0071] It should be noted that the specific composite method of the composite sensing response coating is not particularly limited in the embodiment of the present application, and can be selected according to the material properties of the sensing response coating. For example, the polymer functional coating can be coated by various physical coating methods such as dipping, spraying, spin coating, and drip coating; the ion functional coating can be coated by electrochemical deposition, so that the functional material can be evenly attached to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle.

[0072] Application Example: By twisting at least two strands of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers into wrinkled entangled structure fiber bundles, and then directly composite the sensor response coating, a highly sensitive MXene-based sensor fiber can be prepared. On the one hand, the wrinkled entangled fiber bundle structure formed by twisting can provide more charge transfer channels, a larger specific surface area and contact area, which is beneficial to improve the conductivity and the adhesion amount of the sensor response coating material, thereby significantly enhancing the sensing of environmental and human physiological signals, making the titanium carbide / PEDOT / polyrotaxane sensor fiber have higher sensitivity. and shorter response time; on the other hand, the dynamic pulley effect produced by the rich adjustable porous structure, titanium carbide / PEDOT rigid interface structure and titanium carbide / polyrotaxane dynamic pulley interface structure in the titanium carbide / PEDOT / polyrotaxane composite fiber structure can synergize with the wrinkled entanglement structure of the twisted fiber bundle, effectively enhancing the flexibility and tensile strength of the titanium carbide / PEDOT / polyrotaxane sensing fiber, making it easy to weave and have good tolerance to mechanical deformation, effectively increasing the service life of the titanium carbide / PEDOT / polyrotaxane sensing fiber, and significantly improving the user experience.

[0073] The present application embodiment provides a method for preparing a wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber, preferably comprising the following steps:

[0074] Wet spinning a mixed dispersion containing titanium carbide, (PEDOT:PSS) and polyrotaxane to obtain primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fibers;

[0075] The primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fiber is subjected to chemical crosslinking, electrostatic coupling, hot pressing and vacuum drying in sequence to obtain wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers.

[0076] Among them, the preparation method of the embodiment of the present application can make the titanium carbide / PEDOT / polyrotaxane composite fiber form a double-interface internal structure of "both the dynamic roller skating interface of titanium carbide / polyrotaxane and the rigid interface of titanium carbide / PEDOT", so that the titanium carbide / PEDOT / polyrotaxane composite fiber has excellent load-bearing capacity for tensile deformation, and has good tensile strength, elongation at break and flexibility, thereby improving the service life of the titanium carbide / PEDOT / polyrotaxane sensing fiber; at the same time, the primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fiber can form a highly wrinkled structure and a rich adjustable porous structure based on phase separation and shrinkage mechanism during chemical crosslinking, electrostatic chelation and hot pressing, effectively increase the charge transfer channel and is conducive to increasing the load capacity and adhesion of the sensing response coating material, effectively improving the conductivity and sensitivity of the titanium carbide / PEDOT / polyrotaxane sensing fiber.

[0077] In the exemplary description of the embodiment of the present application, the preparation method of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber may include the following steps:

[0078] Step 1: Weigh 0.15g of titanium carbide with a layer of about 1-2μm into a beaker, add 10mL of deionized water, and ultrasonicate for 20 minutes to obtain a uniformly dispersed titanium carbide dispersion. After centrifugation and concentration, 150mg / mL of Ti 3 C 2 T X Dispersion liquid;

[0079] Step 2: After PEDOT:PSS is concentrated and filtered, it is added to the Ti 3 C 2 T x The dispersion was vortexed at room temperature for 3 hours to obtain a titanium carbide / (PEDOT:PSS) mixed aqueous dispersion, wherein the solid content of PEDOT:PSS was 10.5 mg;

[0080] Step 3: Weigh 30 mg of polyisoprene / α-cyclodextrin (α-cyclodextrin coverage is 3%) and add it to 200 μL of water, and ultrasonicate for 20 minutes to obtain a 300 mg / mL polyrotaxane aqueous dispersion;

[0081] Step 4: adding the polyrotaxane aqueous dispersion to the titanium carbide / (PEDOT:PSS) mixed aqueous dispersion, vortexing at room temperature for 3 hours to obtain a titanium carbide / (PEDOT:PSS) / polyrotaxane liquid crystal mixed dispersion;

[0082] Step 5: Extruding the titanium carbide / (PEDOT:PSS) / polyrotaxane liquid crystal dispersion through a spinning die, coagulating in an acetic acid coagulation bath, and collecting on a roller to obtain primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fibers;

[0083] Step six: immerse the primary titanium carbide / (PEDOT: PSS) / polyrotaxane composite fiber in a dimethyl sulfoxide solution containing N, N′-carbonyldiimidazole, and soak it at 50°C for 40 minutes, then immerse it in a methanol cleaning bath for 20 minutes, and finally transfer it to a hot pressing device at 70°C, hot press it at a pressure of 1 kPa for 6 minutes, collect it, and place it in a 130°C oven for vacuum heating and drying for 80 minutes to obtain titanium carbide / PEDOT / polyrotaxane composite fiber.

[0084] in, Figure 1 A planar electron microscope scanning image of titanium carbide / PEDOT / polyrotaxane composite fibers is shown.

[0085] according to Figure 1 It can be seen that the titanium carbide / PEDOT / polyrotaxane composite fiber has a highly wrinkled structure, which is very beneficial for improving the sensing response coating and buffering tensile deformation.

[0086] Of course, the above specific example is only a feasible solution for preparing wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments in the embodiment of the present application. Other feasible solutions of solvents and process parameters including the above specific example steps can also be used, which will not be described in detail in the embodiment of the present application.

[0087] In the embodiment of the present application, the sensing response coating preferably includes a pressure response coating, a temperature response coating, an ion response coating, a pH response coating or a glucose response coating. Among them, the pressure response coating refers to a functional layer that can cause a change in capacitance based on the change in dielectric layer thickness and contact area when subjected to external pressure; the temperature response coating refers to a functional layer that can cause volume expansion due to an increase in intermolecular distance, a phase change, or the expansion of the molecule itself after being subjected to external thermal stimulation; the ion response coating refers to a functional layer that can cause an electrode potential change based on an ion concentration difference; the glucose response coating refers to a functional layer that can cause a peak current change based on a change in glucose content; and the pH response coating refers to a functional layer that can cause a peak potential change as the pH increases.

[0088] In an embodiment of the present application, the pressure-responsive coating is preferably formed by a dielectric polymer, and the dielectric polymer is preferably at least one of polyurethane (PU), polydimethylsiloxane (PDMS), polyimide (PI) or polyvinylidene fluoride (PVDF).

[0089] It should be noted that the pressure-responsive coating formed by the dielectric polymer can be formed by physical coating methods such as dipping, spraying, and spin coating. The embodiments of the present application do not limit the specific coating method, and those skilled in the art can choose according to actual needs. For example, when the embodiment of the present application selects the dipping method, the dielectric polymer can be dissolved in a good solvent to prepare a dielectric polymer solution with a mass concentration of 6 to 60wt%, and then the titanium carbide / PEDOT / polyrotaxane structure fiber bundle is soaked in the dielectric polymer solution, so that a layer of dielectric polymer is evenly attached to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle, that is, a pressure-responsive coating is constructed. Among them, the embodiments of the present application do not limit the dipping time and number of dipping times of the dielectric polymer, and those skilled in the art can reasonably set them according to needs.

[0090] In the embodiment of the present application, the temperature responsive coating is preferably formed by a thermoresponsive polymer, and the thermoresponsive polymer is preferably at least one of polyethylene oxides of different molecular weights or mixtures thereof, polyethylene glycol methacrylate, polyethylene glycol acrylate, poly(N-isopropylacrylamide) or paraffin. Wherein, the polyethylene oxides of different molecular weights or mixtures thereof refer to polyethylene oxides of different molecular weights or mixtures of polyethylene oxides of different molecular weights.

[0091] It should be noted that the temperature responsive coating formed by the thermally responsive polymer can be formed by physical coating methods such as dipping, spraying, and spin coating. The embodiments of the present application do not limit the specific coating method, and those skilled in the art can choose according to actual needs. For example, when the embodiment of the present application selects the dipping method, the thermally responsive polymer can be dissolved in a good solvent to prepare a thermally responsive polymer solution with a mass concentration of 0.1 to 40wt%, and then the titanium carbide / PEDOT / polyrotaxane structure fiber bundle is soaked in the thermally responsive polymer solution, so that a layer of thermally responsive polymer is evenly attached to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle, and a temperature responsive coating is obtained. Among them, the embodiments of the present application do not specifically limit the dipping time, dipping times, etc. of the thermally responsive polymer, and those skilled in the art can reasonably set them according to needs.

[0092] In the embodiment of the present application, the ion-responsive coating sequentially comprises a (PEDOT:PSS) conductive layer and an ion selective membrane composited on the (PEDOT:PSS) conductive layer, and the precursor for preparing the ion selective membrane is preferably a mixture of sodium tetraphenylborate, polyvinyl chloride, dioctyl sebacate and an ion carrier, wherein the ion carrier can be Na + , K + , Ca 2+ ,Mg 2+ , Zn 2+ At least one of .

[0093] It should be noted that the (PEDOT:PSS) conductive layer can be formed by physical coating methods such as dip coating, spray coating, and spin coating. The embodiments of the present application do not limit the specific coating method, and those skilled in the art can choose according to actual needs. For example, (PEDOT:PSS) with a mass concentration of 5 to 25 mg / mL can be spin-coated on the titanium carbide / PEDOT / polyrotaxane structure fiber bundle, so that a layer of (PEDOT:PSS) is evenly attached to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle, and a (PEDOT:PSS) conductive layer is obtained; the formation of the ion selective membrane can make the ion selective membrane precursor solution evenly attached to the (PEDOT:PSS) conductive layer to form an ion selective membrane. The ion selective membrane precursor solution can be a tetrahydrofuran mixed solution of sodium tetraphenylborate (0.001-0.03 mg / mL), polyvinyl chloride (0.06-0.7 mg / mL), dioctyl sebacate (0.1-0.3 mg / mL) and ion carrier (0.002-0.06 mg / mL) which is sealed and stored overnight at 4°C and dried.

[0094] In the embodiment of the present application, the glucose responsive coating comprises a zinc oxide nanorod coating and a metal nanoparticle or transition metal oxide coating composited on the zinc oxide nanorod coating. The metal nanoparticle is at least one of Cu, Pt, Au, Ag, Ni, and Pd; the transition metal oxide is CuO, NiO, Cu 2 O, Fe 3 O 4 At least one of .

[0095] It should be noted that the zinc oxide nanorod coating can be obtained by electrochemical deposition by chronoamperometry. For example, the embodiment of the present application preferably uses a mixed solution of 0.01-1 mol / L zinc nitrate hexahydrate and 0.1-5 mol / L potassium chloride as the electrochemical deposition solution, the titanium carbide / PEDOT / polyrotaxane structure fiber bundle as the working electrode, the saturated calomel electrode as the reference electrode, the metal platinum sheet electrode as the counter electrode, the working electrode and the counter electrode are kept at a distance of 3 cm, and the electrochemical deposition is performed by chronoamperometry at a temperature of 40-120°C, the voltage is preferably -0.8-1.0V, and the deposition time is preferably 800-6000s. The metal nanoparticles or transition metal oxide coating can be obtained by electrochemical deposition by chronoamperometry. For example, the embodiment of the present application preferably uses a titanium carbide / PEDOT / polyrotaxane structure fiber bundle with a zinc oxide nanorod coating deposited on the surface as a working electrode, commercial silver / silver chloride as a reference electrode, and a metal platinum sheet electrode as a counter electrode. The distance between the working electrode and the counter electrode is 3 cm. Metal nanoparticles or transition metal oxides are deposited by chronoamperometry at room temperature. The voltage is preferably -0.3 to -0.9 V, and the deposition time is 50 to 500 s.

[0096] In the embodiment of the present application, the pH responsive coating is preferably formed by a conductive polymer, and the conductive polymer is preferably at least one of polyaniline, poly (2,5) -dimethylaniline and poly (4,4) -benzidine.

[0097] It should be noted that the conductive polymer can be formed into a pH-responsive coating by electrochemical deposition or physical coating methods such as dipping, spraying, and spin coating. The present application embodiment does not limit this, and those skilled in the art can choose according to actual needs. For example, in the present application embodiment, a mixed solution of 0.1 to 1 M aniline and 0.1 to 1 M sulfuric acid is used as an electrochemical deposition solution, the titanium carbide / PEDOT / polyrotaxane structure fiber bundle is used as a working electrode, a metal platinum sheet electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. In the voltage window of -0.2 V to 1.0 V, cyclic voltammetry is used for electrodeposition for 10 to 200 cycles to obtain a pH-responsive coating.

[0098] In the second aspect, as a specific example of the highly sensitive MXene-based sensing fiber described above, the embodiment of the present application further provides a method for preparing a highly sensitive MXene-based pressure sensing fiber, which preferably includes:

[0099] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0100] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0101] After preparing a dielectric polymer into a dielectric polymer solution with a mass concentration of 6 to 60%, the dielectric polymer solution is uniformly coated on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a MXene-based structure fiber bundle with a surface composite dielectric layer;

[0102] At least two strands of the MXene-based structural fiber bundles with the surface composite dielectric layer are twisted to obtain a highly sensitive MXene-based pressure sensing fiber.

[0103] It should be noted that, in the embodiment of the present application, after twisting at least two strands of the corrugated titanium carbide / PEDOT / polyrotaxane composite fibers to form a corrugated entangled structural fiber bundle, a dielectric polymer solution with a mass concentration of 6 to 60% is directly coated so that the dielectric polymer coating is evenly attached to the surface of the corrugated entangled structural fiber bundle. In view of this, when the titanium carbide / PEDOT / polyrotaxane structure fiber bundle with a composite dielectric polymer coating is subjected to external pressure, the thickness and contact area of ​​the dielectric polymer coating change accordingly and cause a change in capacitance, thereby detecting pressure stimulation based on the feedback of capacitance change; at the same time, the combined effect of the highly wrinkled structure of the fiber filaments and the entangled and twisted structure of the fiber bundle effectively enhances the capacitance response under force stimulation; in addition, the rich porous structure inside the titanium carbide / PEDOT / polyrotaxane composite fiber structure and the pores between the titanium carbide / PEDOT / polyrotaxane composite fiber and the dielectric polymer coating can provide deformation space, thereby making the deformation under the action of external force more significant, which is beneficial to enhancing the capacitance response, making the pressure response of the titanium carbide / PEDOT / polyrotaxane pressure sensing fiber more sensitive.

[0104] In the third aspect, as a specific example of the highly sensitive MXene-based sensing fiber described above, the embodiment of the present application further provides a method for preparing a highly sensitive MXene-based temperature sensing fiber, which preferably includes:

[0105] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0106] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0107] The titanium carbide / PEDOT / polyrotaxane structure fiber bundle is immersed in a thermal responsive polymer solution for 0.5 to 10 minutes, taken out and naturally dried, and the operation is repeated 1 to 8 times to obtain a highly sensitive MXene-based temperature sensing fiber.

[0108] It should be noted that, in the embodiment of the present application, after twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments to form a wrinkled entangled structure fiber bundle, the thermal responsive polymer solution is repeatedly coated and dried, so that the surface of the wrinkled entangled structure fiber bundle is evenly attached with a thermal responsive polymer coating. In view of this, after the titanium carbide / PEDOT / polyrotaxane structure fiber bundle with a composite thermal responsive polymer coating is subjected to external thermal stimulation, the thermal responsive polymer will cause the thermal responsive coating volume to expand due to the increase in the intermolecular distance, phase change or the expansion of the molecule itself, thereby causing the spacing between the fiber filaments in the wrinkled entangled structure fiber bundle to increase, resulting in an increase in the internal resistance of the wrinkled entangled structure fiber bundle, and the feedback of temperature change information can be realized based on the thermal resistance effect; at the same time, the highly wrinkled surface structure and high conductivity can enhance the thermal resistance effect, which is beneficial to improve the temperature response sensitivity of the titanium carbide / PEDOT / polyrotaxane temperature sensing fiber.

[0109] In the fourth aspect, as a specific example of the highly sensitive MXene-based sensing fiber described above, the embodiment of the present application further provides a method for preparing a highly sensitive MXene-based ion sensing fiber, which preferably includes:

[0110] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0111] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0112] The surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle is uniformly coated with a (PEDOT:PSS) conductive layer to obtain a MXene-based structure fiber bundle with a surface composite conductive layer;

[0113] After preparing an ion selective membrane precursor solution containing sodium tetraphenylborate, polyvinyl chloride, dioctyl sebacate and ion carrier, the ion selective membrane precursor solution is dripped onto the surface of the MXene-based structural fiber bundle of the surface composite conductive layer, and dried naturally to obtain a highly sensitive MXene-based ion sensing fiber.

[0114] It should be noted that, in the embodiment of the present application, after twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to form a wrinkled entangled structure fiber bundle, the (PEDOT:PSS) conductive layer and the ion selective membrane are coated in sequence, so that the surface of the wrinkled entangled structure fiber bundle is evenly attached to the (PEDOT:PSS) conductive layer and the ion selective membrane from the inside to the outside. In view of this, when the ion selective membrane contacts the solution to be tested, the difference in ion concentration inside and outside the ion selective membrane will cause a change in the electrode potential, and the concentration of specific ions in the solution can be determined by measuring the potential change of the electrode and according to the Nernst equation. At the same time, due to the wrinkled entangled structure of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle, the adhesion of the ion selective membrane, the coating amount and the uniformity of the coating are effectively increased, so that the titanium carbide / PEDOT / polyrotaxane ion sensing fiber can show high ion sensitivity.

[0115] In the fifth aspect, as a specific example of the highly sensitive MXene-based sensing fiber described above, the embodiment of the present application further provides a method for preparing a highly sensitive MXene-based pH sensing fiber, which preferably includes:

[0116] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0117] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0118] In a three-electrode system, cyclic voltammetry was used to deposit a conductive polymer on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a highly sensitive MXene-based pH sensing fiber.

[0119] It should be noted that, in the present embodiment, after twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments to form a wrinkled entangled fiber bundle structure, a conductive polymer coating is electrochemically deposited on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle using cyclic voltammetry. Therefore, the conductive polymer reacts with H in the solution to be tested under acidic conditions. + When the reaction occurs, the electron cloud of the conductive polymer will be rearranged, which will eventually cause the change of the potential signal and make its peak potential decrease with the increase of pH. The corresponding pH value can be determined by monitoring the peak potential value. At the same time, the highly wrinkled and entangled structure of the titanium carbide / PEDOT / polyrotaxane fiber bundle effectively increases the deposition amount of the conductive polymer, making it more sensitive to H + The sensitivity of ionic interaction is improved, so that the titanium carbide / PEDOT / polyrotaxane pH sensing fiber can show high pH sensitivity.

[0120] In a sixth aspect, as a specific example of the highly sensitive MXene-based sensing fiber described above, the embodiment of the present application further provides a method for preparing a highly sensitive MXene-based glucose sensing fiber, the method preferably comprising:

[0121] Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers;

[0122] Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle;

[0123] In a three-electrode system, zinc oxide nanorods are deposited on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle by using a chronoamperometry method to obtain a MXene-based structure fiber bundle with a zinc oxide nanorod coating deposited on the surface;

[0124] The metal nanoparticles and / or transition metal oxide coating are deposited on the surface of the MXene-based structural fiber bundle on which the zinc oxide nanorod coating is deposited by chronoamperometry to obtain a high-sensitivity MXene-based glucose sensing fiber.

[0125] It should be noted that, in the embodiment of the present application, after twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments to form a wrinkled entangled structure fiber bundle, a zinc oxide nanorod coating and a metal nanoparticle / or transition metal oxide coating are electrochemically deposited from the inside to the outside on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle by cyclic voltammetry. Among them, the zinc oxide nanorod is a nanomaterial with good compatibility with biomacromolecules (isoelectric point is 9.5), and the isoelectric point of protein molecules is low. Under the action of electrostatics, the two adsorb each other, so that the electrochemical activity and electron transfer efficiency of the electrode can be improved; and the metal nanoparticles or metal oxides can be used as solid-phase catalysts to catalyze the oxidation of glucose dissolved in water to gluconolactone, which is specifically reflected in the cyclic voltammogram as a pair of redox peaks with higher potentials. As the glucose content in the solution increases, the peak current gradually increases, and the glucose content in the solution can be determined by measuring the current value. In addition, the highly wrinkled and entangled structure of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle effectively increases the electrodeposition amount of zinc oxide nanorods and metal nanoparticles or metal oxides, thereby enabling the titanium carbide / PEDOT / polyrotaxane glucose sensing fibers to show high glucose sensitivity.

[0126] In the seventh aspect, the embodiments of the present application also provide the above-mentioned high-sensitivity MXene-based pressure sensing fiber, high-sensitivity MXene-based temperature sensing fiber, high-sensitivity MXene-based ion sensing fiber, high-sensitivity MXene-based pH sensing fiber and high-sensitivity MXene-based glucose sensing fiber for use in the preparation of multifunctional sensing integrated flexible fabrics. Among them, since the sensing fiber of the embodiment of the present application has the advantages of high sensitivity, good flexibility and mechanical deformation tolerance, after the sensing fiber of the embodiment of the present application is used to prepare a multifunctional sensing integrated flexible fabric, the multifunctional sensing integrated flexible fabric can show high sensitivity, high linearity, high accuracy and no crosstalk between monitoring signals, and has good application prospects.

[0127] Example 1: Preparation of Titanium Carbide / PEDOT / Polyrotaxane Pressure Sensing Fiber (PSF)

[0128] Example 1: Preparation of titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PU), comprising the following steps:

[0129] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0130] In a twisting device, three strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted five times to form a fiber bundle;

[0131] A polyurethane aqueous solution with a concentration of 28 wt % was uniformly coated on the surface of the fiber bundle, and two fiber bundles coated with polyurethane were twisted with each other to obtain titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PU).

[0132] in, Figure 2 An electron micrograph of a twisted 3-strand wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber is shown; Figure 3 The capacitance change rate of titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PU) under different pressures is shown.

[0133] according to Figure 2 It can be seen that the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers have good flexibility and will not be damaged or broken by twisting and torsion operations. In addition, there are large porous gaps between the twisted fiber bundles, which is beneficial to increase the deposition and coating amount of the sensor response coating.

[0134] according to Figure 3 It can be seen that titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PU) exhibits excellent responsiveness to external pressure stimuli, and still has good responsiveness even under a pressure of 0.002N.

[0135] Example 2: Preparation of titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PDMS), comprising the following steps:

[0136] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0137] In a twisting device, 10 strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted 5 times to form a fiber bundle;

[0138] A polydimethylsiloxane / tetrahydrofuran solution with a concentration of 35 wt % was uniformly coated on the surface of the fiber bundle, and four fiber bundles coated with polydimethylsiloxane were twisted with each other to obtain titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PDMS).

[0139] Example 3: Preparation of titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PVDF), comprising the following steps:

[0140] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0141] In a twisting device, 10 strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted 6 times to form a fiber bundle;

[0142] A 25% polyvinylidene fluoride / dimethylformamide solution was uniformly coated on the surface of the fiber bundle, and six strands of fiber bundles coated with polydimethylsiloxane were twisted with each other to obtain titanium carbide / PEDOT / polyrotaxane pressure sensing fiber (PSF-PVDF).

[0143] Example 2: Preparation of Titanium Carbide / PEDOT / Polyrotaxane Temperature Sensing Fiber (TSF)

[0144] Example 1: Preparation of titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-PEO), comprising the following steps:

[0145] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0146] In a twisting device, three strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted six times to form a fiber bundle;

[0147] The fiber bundle was immersed in an 80 mg / mL polyethylene oxide (PEO, Mw=1.5 kg / mol) aqueous solution for 3 minutes, and then taken out and dried; the "immersion-drying" operation was repeated 3 times to obtain titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-PEO).

[0148] in, Figure 4 The resistance change rate of titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-PEO) at different temperatures is shown.

[0149] according to Figure 4 It can be seen that titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-PEO) exhibits excellent temperature-sensitive properties, can detect small changes of 0.1°C, and has good temperature responsiveness.

[0150] Example 2: Preparation of titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-MSDS), comprising the following steps:

[0151] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0152] In a twisting device, 8 strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted 5 times to form a fiber bundle;

[0153] The fiber bundle was immersed in a 100 mg / mL 10% polyethylene glycol methacrylate / ethanol solution for 3 minutes, and then taken out and dried; the "immersion-drying" operation was repeated 5 times to obtain a titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-MSDS).

[0154] Example 3: Titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-PEO m ) is prepared, comprising the steps of:

[0155] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0156] In a twisting device, nine strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted six times to form a fiber bundle;

[0157] The fiber bundle was immersed in a solution containing 45 mg / 2 mL of PEO (Mw=1.5 kg / mol) and 9 mg / 2 mL of PEO. 2 The titanium carbide / PEDOT / polyrotaxane temperature sensing fiber (TSF-PEO m ).

[0158] Example 3: Preparation of Titanium Carbide / PEDOT / Polyrotaxane pH Sensing Fiber

[0159] Example 1: Preparation of titanium carbide / PEDOT / polyrotaxane pH sensing fiber (pH-SF-A), comprising the following steps:

[0160] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0161] In a twisting device, four strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted six times to form a fiber bundle;

[0162] A mixed solution of 0.1 M aniline monomer and 0.1 M sulfuric acid was prepared as an electrolyte, and polyaniline was deposited on the surface of the fiber bundle by electrochemical cyclic voltammetry, wherein the voltage window set by the cyclic voltammetry was -0.2 V to 1.0 V, and the number of electrodeposition scans set was 30. After the electrodeposition was completed, the fiber was washed with clean water to obtain a titanium carbide / PEDOT / polyrotaxane pH sensing fiber (pH-SF-A).

[0163] in, Figure 5 The voltage response results of titanium carbide / PEDOT / polyrotaxane pH sensing fiber (pH-SF-A) in different pH solutions are shown.

[0164] according to Figure 5 It can be seen that the titanium carbide / PEDOT / polyrotaxane pH sensing fiber (pH-SF-A) has an obvious gradient response in the pH range of 4 to 7 and has good pH detection function.

[0165] Example 2: Preparation of titanium carbide / PEDOT / polyrotaxane pH sensing fiber (pH-SF-DA), comprising the following steps:

[0166] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0167] In a twisting device, eight strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted six times to form a fiber bundle;

[0168] A mixed solution of 0.3 M (4,4) benzidine monomer and 0.3 M sulfuric acid was prepared as an electrolyte, and (4,4) benzidine was deposited on the surface of the fiber bundle by electrochemical cyclic voltammetry, wherein the voltage window set in the cyclic voltammetry method was -0.2 V to 1.0 V, and the number of electrodeposition scans was set to 20. After the electrodeposition was completed, the fiber was washed with clean water to obtain a titanium carbide / PEDOT / polyrotaxane pH sensing fiber (pH-SF-DA).

[0169] Example 4: Preparation of Titanium Carbide / PEDOT / Polyrotaxane Ion Sensing Fiber (SF-ion)

[0170] Example 1: Titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Na + ) is prepared, comprising the steps of:

[0171] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0172] In a twisting device, three strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted three times to form a fiber bundle;

[0173] A 15 mg / mL (PEDOT:PSS) conductive layer was drop-coated on the fiber bundle surface to obtain a MXene-based structured fiber bundle with a surface composite conductive layer. 0.7 mg tetrasodium salt [3,5-bis(trifluoromethylphenyl)] borate (NaSFPB), 40 mg high molecular weight polyvinyl chloride (PVC), 70 mg bis(2-ethylhexyl) sebacate (DOS) and 1.2 mg Na + The ion carrier was dissolved in 500uL tetrahydrofuran to obtain Na + Ion selective membrane precursor solution, then Na + The ion selective membrane precursor solution is uniformly coated on the surface of the MXene-based structure fiber bundle with the surface composite conductive layer to obtain the titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Na + ).

[0174] in, Figure 6 The titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Na + ) Voltage response test results in sodium ion solutions with different concentrations.

[0175] according to Figure 6 It can be seen that with the change of ion concentration in the solution, the titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Na + ) can respond instantly, even under a concentration change of 5mM; and it shows excellent responsiveness in a wide detection range of 5 to 30mM.

[0176] Example 2: Titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Ca 2+ ) is prepared, comprising the steps of:

[0177] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0178] In a twisting device, three strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted three times to form a fiber bundle;

[0179] A 15 mg / mL PEDOT:PSS conductive layer was drop-coated on the fiber bundle surface to obtain a MXene-based fiber bundle with a surface composite conductive layer. 1 mg tetrasodium salt [3,5-bis(trifluoromethylphenyl)] borate (NaSFPB), 50 mg high molecular weight polyvinyl chloride (PVC), 80 mg bis(2-ethylhexyl) sebacate (DOS) and 3 mg Ca 2+ The ion carrier was dissolved in 500uL tetrahydrofuran to obtain Ca 2+ Ion selective membrane precursor solution. Then, Ca 2+ The ion selective membrane precursor solution was uniformly coated on the surface of the MXene-based structure fiber bundle with a surface composite conductive layer to obtain titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Ca 2+ ).

[0180] in, Figure 7 The titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Ca 2+ ) Voltage response detection results in solutions with different calcium ion concentrations.

[0181] according to Figure 7 It can be seen that titanium carbide / PEDOT / polyrotaxane ion sensing fiber (SF-Ca 2+ ) can respond instantly in a wide detection range (0.5-2.5 mM) and has a low detection line (0.5 mM), showing excellent Ca 2+ Responsiveness.

[0182] Example 5: Preparation of Titanium Carbide / PEDOT / Polyrotaxane Glucose Sensing Fiber (SF-Glu)

[0183] Example 1: Preparation of titanium carbide / PEDOT / polyrotaxane glucose sensing fiber (SF-Glu-Cu), comprising the following steps:

[0184] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0185] In a twisting device, three strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted three times to form a fiber bundle;

[0186] In a three-electrode system, a mixed solution of 0.05 mol / L zinc nitrate hexahydrate and 0.6 mol / L potassium chloride was used as the electrochemical deposition solution, the fiber bundle was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the metal platinum sheet electrode was used as the counter electrode. The distance between the working electrode and the counter electrode was 3 cm. After electrochemical deposition for 2000 s by chronoamperometry at a temperature of 60 ° C and a voltage of -0.8 V, the fiber bundle was washed with a large amount of double distilled water and dried at room temperature to obtain a fiber bundle with ZnO nanorods deposited on the surface. Subsequently, 0.01 mol / L CuSO 4 ·5H 2 O and 0.1 mol / L NaSO 4 The mixed solution was used as the electrochemical deposition solution, the fiber bundle with ZnO nanorods deposited on the surface was used as the working electrode, commercial silver / silver chloride was used as the reference electrode, and the metal platinum sheet electrode was used as the counter electrode. The distance between the working electrode and the counter electrode was 3 cm. The deposition was carried out by chronoamperometry at room temperature and a voltage of -0.3 V for 200 s, and finally rinsed with distilled water to obtain titanium carbide / PEDOT / polyrotaxane glucose sensing fiber (SF-Glu-Cu).

[0187] in, Figure 8 The current response of titanium carbide / PEDOT / polyrotaxane glucose sensing fiber (SF-Glu-Cu) in glucose solutions with different concentrations is shown.

[0188] according to Figure 8 It can be seen that titanium carbide / PEDOT / polyrotaxane glucose sensing fiber (SF-Glu-Cu) exhibits fast and immediate glucose response characteristics and can quickly reach a stable state, showing excellent glucose response performance.

[0189] Example 2: Preparation of titanium carbide / PEDOT / polyrotaxane glucose sensing fiber (SF-Glu-Ni), comprising the following steps:

[0190] The wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber was prepared according to the exemplary method described above;

[0191] In a twisting device, three strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments are twisted three times to form a fiber bundle;

[0192] In a three-electrode system, a mixed solution of 0.01 mol / L zinc nitrate hexahydrate and 0.3 mol / L potassium chloride was used as the electrochemical deposition solution, the fiber bundle was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the metal platinum sheet electrode was used as the counter electrode. The distance between the working electrode and the counter electrode was kept at 3 cm. After electrochemical deposition for 3000 s by chronoamperometry at a temperature of 80°C and a voltage of -1 V, the fiber bundle with ZnO nanorods deposited on the surface was obtained after being fully washed with double distilled water and dried at room temperature. Afterwards, a mixed solution of 1 mol / L nickel chloride and 0.1 mol / L sodium acetate was used as the electrochemical deposition solution, the fiber bundle with ZnO nanorods deposited on the surface was used as the working electrode, commercial silver / silver chloride was used as the reference electrode, and the metal platinum sheet electrode was used as the counter electrode. The distance between the working electrode and the counter electrode was maintained at 3 cm. The deposition was carried out by chronoamperometry at room temperature and a voltage of -0.8 V for 500 s. Finally, the fiber was rinsed with distilled water to obtain titanium carbide / PEDOT / polyrotaxane glucose sensing fiber (SF-Glu-Ni).

[0193] The various embodiments in this specification are described in a progressive manner, and the same or similar parts between the various embodiments can be referenced to each other, and each embodiment focuses on the differences from other embodiments.

[0194] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that the technical solutions recorded in the aforementioned embodiments may still be modified, or some or all of the technical features therein may be replaced by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the present application.

Claims

1. A method for preparing a highly sensitive MXene-based sensing fiber, characterized in that: The steps include: Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers; Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber filaments to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle; A composite sensing response coating is applied to the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a highly sensitive MXene-based sensing fiber; Wherein, the preparation method of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fiber comprises: Wet spinning a mixed dispersion containing titanium carbide, (PEDOT:PSS) and polyrotaxane to obtain primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fibers; The primary titanium carbide / (PEDOT:PSS) / polyrotaxane composite fiber is subjected to chemical crosslinking, electrostatic coupling, hot pressing and vacuum drying in sequence to obtain wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers.

2. The preparation method according to claim 1, characterized in that: The sensor response coating includes a pressure response coating, a temperature response coating, an ion response coating, a glucose response coating and a pH response coating.

3. The preparation method according to claim 2, characterized in that: The pressure responsive coating is formed by a dielectric polymer; The dielectric polymer includes at least one of polyurethane, polydimethylsiloxane, polyvinylidene fluoride, and polyimide; and / or, the temperature responsive coating is formed by a thermoresponsive polymer; The thermoresponsive polymer comprises at least one of polyethylene oxides of different molecular weights or mixtures thereof, polyethylene glycol methacrylate, polyethylene glycol acrylate, poly(N-isopropylacrylamide), and paraffin; And / or, the ion-responsive coating sequentially comprises a (PEDOT:PSS) conductive layer and an ion-selective membrane composited on the (PEDOT:PSS) conductive layer; The ion selective membrane precursor is a mixture of sodium tetraphenylborate, polyvinyl chloride, dioctyl sebacate and ion carrier; And / or, the glucose responsive coating sequentially comprises a zinc oxide nanorod coating and a metal nanoparticle or transition metal oxide coating composited on the zinc oxide nanorod coating; The metal nanoparticles are at least one of Cu, Pt, Au, Ag, Ni, and Pd; the transition metal oxide is at least one of CuO, NiO, Cu2O, and Fe3O4; and / or, the pH responsive coating is formed by a conductive polymer; The conductive polymer includes at least one of polyaniline, poly(2,5)-dimethylaniline and poly(4,4)-benzidine.

4. A method for preparing the highly sensitive MXene-based pressure sensing fiber according to claim 1, characterized in that: The steps include: Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers; Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle; After preparing a dielectric polymer into a dielectric polymer solution with a mass concentration of 6-60%, the dielectric polymer solution is uniformly coated on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a MXene-based structure fiber bundle with a surface composite dielectric layer; At least two strands of the MXene-based structural fiber bundles with the surface composite dielectric layer are twisted to obtain a highly sensitive MXene-based pressure sensing fiber.

5. A method for preparing the highly sensitive MXene-based temperature sensing fiber according to claim 1, characterized in that: The steps include: Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers; Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle; The titanium carbide / PEDOT / polyrotaxane structure fiber bundle is immersed in a thermal responsive polymer solution for 0.5 to 10 minutes, taken out and naturally dried, and the operation is repeated 1 to 8 times to obtain a highly sensitive MXene-based temperature sensing fiber.

6. A method for preparing the highly sensitive MXene-based ion sensing fiber according to claim 1, characterized in that: The steps include: Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers; Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle; The surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle is uniformly coated with a (PEDOT:PSS) conductive layer to obtain a MXene-based structure fiber bundle with a surface composite conductive layer; After preparing an ion selective membrane precursor solution containing sodium tetraphenylborate, polyvinyl chloride, dioctyl sebacate and ion carrier, the ion selective membrane precursor solution is drip-coated on the surface of the MXene-based structural fiber bundle of the surface composite conductive layer, and dried naturally to obtain a highly sensitive MXene-based ion sensing fiber.

7. A method for preparing the highly sensitive MXene-based pH sensing fiber according to claim 1, characterized in that: The steps include: Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers; Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle; In a three-electrode system, cyclic voltammetry was used to deposit a conductive polymer on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle to obtain a highly sensitive MXene-based pH sensing fiber.

8. A method for preparing the highly sensitive MXene-based glucose sensing fiber according to claim 1, characterized in that: The steps include: Preparation of wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers; Twisting at least two strands of the wrinkled titanium carbide / PEDOT / polyrotaxane composite fibers to obtain a titanium carbide / PEDOT / polyrotaxane structure fiber bundle; In a three-electrode system, zinc oxide nanorods are deposited on the surface of the titanium carbide / PEDOT / polyrotaxane structure fiber bundle by using a chronoamperometry method to obtain a MXene-based structure fiber bundle with a zinc oxide nanorod coating deposited on the surface; The metal nanoparticles and / or transition metal oxide coating are deposited on the surface of the MXene-based structural fiber bundle on which the zinc oxide nanorod coating is deposited by using the chronoamperometry to obtain a high-sensitivity MXene-based glucose sensing fiber.

9. Application of the sensor fiber prepared by the preparation method according to any one of claims 1 to 8 in preparing multifunctional sensor integrated flexible fabrics.

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