Asymmetric zoned integrated yarn with power generation, energy storage and sensing and preparation method

Abstract

The application discloses an asymmetric partition integrated yarn with power generation, energy storage and sensing, which comprises an energy storage fiber prepared from TPU / MXene / PDA, the energy storage fiber is impregnated with liquid metal, the surface of the energy storage fiber is spirally wound with silver-plated nylon yarn, and the surface of the silver-plated nylon yarn winding layer is deposited with P(VDF-TrFE) / BaTi03, which is called a self-powered layer, and the whole is called an integrated yarn. The application also discloses a preparation method of the asymmetric partition integrated yarn with power generation, energy storage and sensing. The application belongs to the technical field of chemistry, textiles and physics, and solves the problems of intermittent output and high impedance of power generation devices, limited energy density of energy storage devices and external power supply dependence of sensor devices in the prior art. Meanwhile, the problems of mutual interference between power generation and energy storage units, poor hetero-interface compatibility and large charge transfer loss of multi-stage structure in the multifunctional integrated flexible textile device are solved.

Description

Technical Field

[0001] This invention belongs to the interdisciplinary fields of chemistry, textiles, and physics, and relates to an integrated yarn with asymmetric partitions that combines power generation, energy storage, and sensing. This invention also relates to a method for preparing an integrated yarn with asymmetric partitions that combines power generation, energy storage, and sensing. Background Technology

[0002] With the development of flexible electronics technology and the increasing urgency of sustainable energy demands, existing power generation devices suffer from significant drawbacks such as intermittent and high impedance output, limited energy density of energy storage devices, and reliance on external power supplies for sensors. These shortcomings severely restrict the continuous, stable, and self-powered operation of wearable devices. Therefore, research on integrated intelligent textile devices that combine power generation, energy storage, and sensing functions has become an essential path to promote the practical application of flexible wearable devices.

[0003] However, when the self-powered unit and the energy storage unit are integrated into a single yarn, the mechanical and electric fields generated by their simultaneous operation in a confined space exhibit complex coupling effects. The electric field generated by the energy storage unit can interfere with the power generation output signal, and the mechanical deformation caused by human movement can simultaneously affect the output of the self-powered unit and the energy storage performance. These multi-physics coupling problems lead to a decline in the overall performance of the device. At the same time, the heterogeneous integration of multiple materials involved in the device results in poor interface compatibility, which leads to reduced charge transport efficiency, increased interface resistance, and decreased mechanical stability. Furthermore, the orientation and density of the conductive network in the energy storage device, the cross-interface transfer efficiency of the polarized charge in the power generation layer, and the ion transport path of the electrolyte through the power generation layer and the fiber electrode under the asymmetric functional partition structure all lack systematic structural design and performance optimization schemes.

[0004] To address the technical problems of existing integrated flexible textile devices, such as poor output stability due to mutual interference between self-powered units and energy storage units, low charge transfer efficiency and easy delamination failure due to poor compatibility of interfaces of various heterogeneous materials, and large charge transfer loss due to lack of synergistic optimization of multi-level structures, this invention provides an asymmetric partitioned integrated yarn that combines power generation, energy storage and sensing and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to provide an asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing, and its preparation method, thereby solving the problems of intermittent output and high impedance of power generation devices, limited energy density of energy storage devices, and reliance on external power supply for sensor devices in the prior art.

[0006] Another objective of this invention is to provide a method for preparing asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing, thereby solving key technical problems such as mutual interference between power generation and energy storage units, poor compatibility of heterogeneous interfaces, and large charge transfer losses in multi-level structures in integrated flexible textile devices.

[0007] The technical solution adopted in this invention is an integrated yarn with asymmetric partitions that combines power generation, energy storage and sensing. It includes energy storage fibers made of TPU / MXene / PDA, the energy storage fibers are impregnated with liquid metal, and silver-plated nylon yarn is spirally wound on the surface of the energy storage fibers. P(VDF-TrFE) / BaTiO3 is deposited on the surface of the silver-plated nylon yarn winding layer.

[0008] Another technical solution adopted in this invention is a method for preparing an asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing, implemented according to the following steps: Step 1: Prepare MXene intermediates; Step 2: Prepare spinning solution A for the MXene / TPU / PDA system; Step 3: Prepare energy storage fibers of MXene / TPU / PDA; Step 4: Integrate the interface between the energy storage unit and the self-powered unit; Step 5: Prepare spinning solution B for the self-powered unit; Step 6: Prepare the self-powered unit to finally obtain the integrated yarn.

[0009] The beneficial effects of this invention are as follows: A spinning solution is prepared using TPU / MXene / PDA, and energy storage fibers are prepared using a wet spinning process. The energy storage fibers are immersed in liquid metal, utilizing their high conductivity and fluidity to significantly reduce the contact resistance between the self-powered unit and the energy storage unit, ensuring stable and efficient charge transfer at the interface even under bending and stretching. Silver-plated nylon yarn is spirally wound onto the fiber surface to prepare an integrated yarn. Here, the high strength of the energy storage fibers provides support, creating a rigid skeleton for the spiral winding of the silver-plated nylon yarn, allowing for uniform coating on the liquid metal surface. Simultaneously, P(VDF-TrFE) / BaTiO3 is deposited onto the integrated yarn using an electrospinning process to integrate the self-powered unit. The MXene material in the energy storage layer not only enhances the energy storage performance of the integrated yarn but also significantly reduces charge loss by capturing the charge generated by the friction layer, thereby greatly increasing the power generation output voltage. Therefore, by designing asymmetric functional partitions on a single yarn, key technical issues such as mutual interference between power generation and energy storage units, poor compatibility of heterogeneous interfaces, and large charge transfer losses in multi-level structures in flexible textile devices can be addressed, thereby achieving the goal of integrating yarn power generation, energy storage, and sensing functions. Attached Figure Description

[0010] Figure 1 This is a schematic diagram of the process of preparing asymmetric partitioned integrated yarn for power generation, energy storage and sensing by wet spinning and electrospinning according to the present invention; Figure 2This is a perspective view of the asymmetric partitioned integrated yarn structure of the present invention, which combines power generation, energy storage, and sensing. Figure 3 This is an exploded view of the asymmetric partitioned yarn structure of the present invention; Figure 4a This is a magnified image of the fiber surface morphology when the mass ratio of MXene to TPU is 3:7; Figure 4b It shows the surface morphology and magnified view of the cross section; Figure 5 This is a surface morphology diagram of MXene / TPU / PDA fibers when the mass ratio of MXene to TPU is 7:3; Figure 6 This is a diagram of the surface morphology of MXene / TPU / PDA fibers after impregnation with liquid metal; Figure 7a These are comparison diagrams of the electrochemical impedance spectroscopy of fibers; Figure 7b This is a comparison chart of cyclic voltammetry tests on fibers; Figure 7c Comparison of constant current charge-discharge tests on fibers; Figure 8a It shows the surface morphology and magnified image of the integrated yarn; Figure 8b It shows the cross-sectional morphology and enlarged view of the integrated yarn; Figure 9 The images show actual photos of energy storage fibers with a MXene to TPU mass ratio of 7:3, energy storage fibers impregnated with liquid metal and then wound with silver-plated nylon yarn, and integrated yarn. Figure 10a It includes P(VDF-TrFE) yarn without integrated energy storage fibers and without barium titanate in the power generation layer, as well as integrated yarn with integrated energy storage units and barium titanate in the power generation layer. Figure 10b This is the EDS chart of P(VDF-TrFE) yarn; Figure 10c It is the EDS chart of the integrated yarn; Figure 11 These are power generation performance graphs for different concentrations of P(VDF-TrFE); Figure 12 The output voltage of the integrated yarn at different impact frequencies is when the mass ratio of MXene to dopamine hydrochloride is 100:10, the mass ratio of MXene to TPU is 9:1, the concentration of P(VDF-TrFE) is 13%, and the mass ratio of P(VDF-TrFE) to BaTiO3 is 4:1. Figure 13 This is a diagram showing the voltage signal output of the integrated yarn when a person performs actions on different parts of their body.

[0011] In the diagram, 1. Energy storage fiber, 2. Liquid metal, 3. Silver-plated nylon yarn, 4. Self-powered layer. Detailed Implementation

[0012] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0013] Reference Figure 1 , Figure 2 and Figure 3 The principle of this invention for preparing a multifunctional integrated yarn for power generation, energy storage, and sensing based on an asymmetric partitioned structure design is as follows: using an asymmetric functional partitioned structure design as the technical process, firstly, energy storage fiber 1 is prepared using TPU / MXene / PDA, and then liquid metal 2 is impregnated as an energy storage unit to achieve the energy storage performance of the integrated yarn; then, silver-plated nylon yarn 3 is used as the electrode of the self-powered unit and spirally wound on the surface of the energy storage fiber 1; finally, P(VDF-TrFE) / BaTiO3 is deposited on the surface of the silver-plated nylon yarn 3 winding layer, called the self-powered layer 4, to obtain the integrated yarn and achieve the power generation and sensing performance of the integrated yarn.

[0014] The method for preparing the multifunctional integrated yarn for power generation, energy storage, and sensing of the present invention selects components in the following manner: 1) Energy storage fiber 1 with a "sandwich" structure was prepared by wet spinning of TPU / MXene / PDA. TPU represents elastic polyurethane, MXene represents transition metal carbon / nitride, and PDA represents polydopamine; wherein, the mass ratio of MXene to PDA in energy storage fiber 1 is 100:(5~15), and the mass ratio of MXene to TPU is 3:7~9:1.

[0015] This "sandwich" structure utilizes the PDA as a multifunctional adhesive. The catechol groups on its molecular chain form strong coordination / hydrogen bonds with the active sites on the MXene surface, effectively anchoring the MXene sheets and preventing aggregation. Simultaneously, it interacts with the urethane groups in the TPU molecular chain, firmly bonding the MXene to the TPU matrix. This sandwich structure, through the bridging effect of the PDA, achieves stable fixation of MXene and TPU, thus simultaneously obtaining high mechanical strength, high charge storage capacity, and excellent cycling stability.

[0016] 2) The energy storage fiber is impregnated in liquid metal to obtain the energy storage unit, and the interface resistance between the energy storage unit and the self-powered unit is adjusted. The liquid metal impregnated in the TPU / MXene / PDA energy storage fiber is a gallium-indium alloy, and the mass ratio of gallium to indium is (2~3):1.

[0017] Liquid metal utilizes its high fluidity and low modulus to form an adaptive contact layer on the surface of energy storage fibers, filling the micro-nano gaps caused by mechanical deformation in real time, thereby reducing and stabilizing the contact resistance at an extremely low level.

[0018] 3) The silver-plated nylon yarn is spirally wound onto the surface of the impregnated energy storage fiber to prepare the integrated yarn. The resistivity of the silver-plated nylon yarn is 0.3Ω / cm~1Ω / cm, the breaking strength is 15~20cN / dtex, and the silver content is 20%~80%.

[0019] 4) P(VDF-TrFE) / BaTiO3 is deposited on the integrated yarn using an electrospinning process to obtain a self-powered unit, referred to as a self-powered unit.

[0020] In the self-powered unit, P(VDF-TrFE) represents poly(vinylidene fluoride-trifluoroethylene), BaTiO3 represents barium titanate, the concentration of P(VDF-TrFE) solution is 8%-14%, and the mass ratio of P(VDF-TrFE) to BaTiO3 is (3~5):1.

[0021] The selection principle of the above-mentioned components of the integrated yarn of this invention is as follows: TPU in the energy storage fiber has high strength and elasticity, providing excellent mechanical properties for the energy storage fiber. MXene is a functional material; its high conductivity and specific surface area enable the fiber to have energy storage performance. PDA acts as a nano-adhesive to bond the two materials, realizing a "sandwich" structure of fiber layer-by-layer self-assembly. Liquid metal can overcome the interfacial barrier between the self-powered unit and the energy storage unit, realizing efficient transmission and dynamic matching of energy in the generation and storage process. The self-powered unit uses silver-plated nylon yarn as the electrode. P(VDF-TrFE) / BaTiO3 serves as the triboelectric generation layer of the self-powered unit. By leveraging the synergistic optimization of ferroelectric properties and high dielectric constant, an efficient charge trapping network is constructed, endowing the triboelectric layer with extremely high charge storage capacity and output stability. BaTiO3, as a high dielectric constant filler, enhances the dielectric constant and charge trapping capacity of the material, improving triboelectric output. This asymmetric functional partitioning design of a single yarn realizes the yarn structure, integrating power generation, energy storage, and sensing performance into a single yarn.

[0022] As can be seen, the technical solution adopted in this invention is an integrated yarn with asymmetric partitioning that combines power generation, energy storage, and sensing. The asymmetric partitioning structure refers to the energy storage unit as the inner layer, with interface regulation performed on top of the energy storage unit. The power generation unit electrodes are combined with the energy storage unit, and a self-powered unit power generation layer is deposited on top of this as the outer layer. Through this layer-by-layer assembly method from the inside out, the asymmetric partitioning structure design of the integrated yarn is completed, realizing the integration of power generation, energy storage, and power generation functions into a single yarn.

[0023] The method for preparing the integrated yarn of the present invention is carried out using the selected components described above, and is implemented according to the following steps: Step 1: Prepare MXene intermediates. The specific process is as follows: 1.1) Weigh hydrochloric acid, lithium fluoride, and aluminum carbide together and put them into a beaker made of polytetrafluoroethylene material and mix them. The mass ratio of hydrochloric acid to lithium fluoride is (30~15):1, and the mass ratio of lithium fluoride to aluminum carbide is (1~2):1. 1.2) The polytetrafluoroethylene beaker containing the above three substances was stirred in a water bath at 35℃~40℃ for 31h~40h. The etched solution was centrifuged and acid-washed at 3500rpm~4000rpm until pH=6~7. The acid-washed liquid was filtered and dried at 40℃~45℃ for 18h~25h. After sonication for 2h~3h, it was centrifuged and the supernatant was freeze-dried at -70℃~-80℃ for 48h~72h to obtain the MXene intermediate (this MXene intermediate is an easily dispersed aerogel, and the interior is still MXene nanosheets).

[0024] Step 2: Prepare spinning solution A of the MXene / TPU / PDA system. The specific process is as follows: 2.1) Dissolve TPU in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of (4~2):1, and stir at 58℃~63℃ for 5h~6h under sealed conditions to obtain a TPU preparation solution with a concentration of 9%~12%. 2.2) Weigh out MXene intermediate and dopamine hydrochloride in a mass ratio of 100:(5~15) and add them together to the TPU preparation solution. The mass ratio of MXene intermediate to TPU preparation solution is 3:7~9:1. Stir for 2h~4h to obtain spinning mixture. 2.3) After sonicating the spinning mixture in an ice-water bath for 2-3 hours, stir for 30-60 minutes and let it stand for 7-12 hours to obtain the spinning solution A of the MXene / TPU / PDA system.

[0025] Dopamine hydrochloride, as a precursor of PDA, was used to construct the PDA interface layer through an in-situ polymerization strategy to prepare an MXene-PDA-TPU spinning system with a typical "sandwich" structure.

[0026] Step 3: Prepare MXene / TPU / PDA energy storage fibers. The specific process is as follows: Use a 5ml syringe to draw 3ml-5ml of spinning solution A, and use a micro-injection pump to dispense 7ml at a time. -1 ~12mlh -1The spinning solution A was injected into a coagulation bath of deionized water using a circular needle (size 21, inner diameter 0.51 mm) at the specified injection rate. (There is no fixed ratio between the two; the more coagulation bath, the better, with a range of approximately 1:10 to 1:100). The solution was coagulated in the coagulation bath for 20 to 30 minutes. After removal, the solution was dried at room temperature for 3 to 5 hours to obtain MXene / TPU / PDA energy storage fibers.

[0027] Step 4: Integrate the energy storage unit and the self-powered unit at the interface. The specific process is as follows: 4.1) The energy storage fiber of MXene / TPU / PDA is immersed in liquid metal for 2h~3h to form a liquid metal interface on the surface of the energy storage fiber, which is called an energy storage unit; the liquid metal is a gallium-indium alloy with a mass ratio of gallium to indium of (2~3):1; 4.2) Use silver-plated nylon yarn at 30 o ~45 o The spiral winding method is combined with the impregnated energy storage fiber, which is called a self-powered unit. The silver-plated nylon yarn serves as the electrode of the self-powered unit.

[0028] The silver-plated nylon yarn has a silver content of 20% to 80%, a resistivity of 0.3Ω / cm to 1Ω / cm, and a breaking strength of 15 to 20 cN / dtex.

[0029] Step 5: Prepare spinning solution B for the self-powered unit: The preparation process of spinning solution B for the P(VDF-TrFE) / BaTiO3 self-powered unit triboelectric generation layer is as follows: A mixed solvent of N,N-dimethylformamide and acetone was obtained with a mass ratio of 3:2 to 5:3. P(VDF-TrFE) and BaTiO3 were dissolved together in the mixed solvent. The mass concentration of P(VDF-TrFE) in the mixed solvent was 8% to 14%, and the mass ratio of P(VDF-TrFE) to BaTiO3 was (3 to 5):1, thus obtaining spinning solution B.

[0030] Step 6: Prepare the self-powered unit to finally obtain the integrated yarn.

[0031] The fabrication process of the P(VDF-TrFE) / BaTiO3 self-powered unit (i.e., the self-powered unit triboelectric layer) is as follows: Electrospinning solution B was dispensed into two 10ml syringes (conjugate spinning) and secured securely. 23G plastic needles were connected to the positive and negative power supplies, with the distance between the two needle tips being 12cm~15cm. Electrospinning was then performed. The electrospinning parameters were: a fixed flow rate of 0.5~0.55ml / h, positive and negative voltages of 3.5kV~5kV, a disc rotation speed of 500rpm~700rpm, a collecting shaft speed of 1mm / s~2mm / s, a distance between the needle tip and the disc collector of 4cm~6cm, a temperature of 35°C~40°C, and a humidity of 40%RH~50%RH. Then, the yarn prepared by electrospinning is placed in an oven at 70°C~80°C for 2h~3h to finally obtain an integrated yarn with asymmetric partition structure for power generation, energy storage and sensing.

[0032] Example 1 This embodiment 1 follows the steps described above, and the specific process is as follows: Preparatory steps and material selection: TPU in the energy storage unit possesses high strength and elasticity, providing excellent mechanical properties for the energy storage fibers. MXene's high conductivity and specific surface area endow the fibers with energy storage capabilities. PDA acts as a nano-adhesive to bond the two materials, achieving a layer-by-layer self-assembled "sandwich" structure. Liquid metal overcomes the interfacial barrier between the self-powered unit and the energy storage unit, enabling efficient energy transfer and dynamic matching during generation and storage. The self-powered unit uses silver-plated nylon yarn as electrodes, and P(VDF-TrFE) / BaTiO3 as the triboelectric generation layer. BaTiO3, as a high dielectric constant filler, enhances the material's dielectric constant and charge trapping ability, improving triboelectric output.

[0033] Step 1: Preparation of MXene intermediate: Hydrochloric acid and lithium fluoride were mixed in a 30:1 mass ratio, and lithium fluoride and aluminum carbide were mixed in a 1:1 mass ratio in a polytetrafluoroethylene beaker. The three substances were stirred in a water bath at 40°C for 31 h. The etched solution was centrifuged at 4000 rpm and acid-washed until pH=6. The acid-washed liquid was filtered and dried at 40°C for 18 h; the resulting solid was sonicated for 2 h and centrifuged. The supernatant was freeze-dried at -80°C for 48 h to obtain the MXene intermediate.

[0034] Step 2: Preparation of spinning solution A for the MXene / TPU / PDA system: TPU was dissolved in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 4:1, and stirred at 58°C for 5 hours under sealed conditions to prepare a 9% TPU solution. Then, MXene intermediate and dopamine hydrochloride at a mass ratio of 100:5 were added to the TPU solution and stirred for 2 hours. The mass ratio of MXene intermediate to TPU was 3:7. The spinning solution was ultrasonicated in an ice-water bath for 2 hours, stirred for 60 minutes, and allowed to stand for 12 hours to obtain spinning solution A.

[0035] Step 3, Preparation of Energy Storage Fiber: 3 ml of spinning solution A is drawn using a 5 ml syringe, and then injected at a rate of 7 ml / h using a micro-injection pump. -1 At the specified injection rate, spinning solution A was injected into a deionized water coagulation bath using a circular needle (size 21, inner diameter 0.51 mm). After coagulation in the coagulation bath for 30 minutes, the fiber was removed and dried at room temperature for 5 hours to complete the preparation of MXene / TPU / PDA energy storage fibers. The surface morphology and cross-sectional morphology of the MXene / TPU / PDA energy storage fibers are shown in the figure. Figure 4a , Figure 4b As shown, it can be observed that when the MXene loading is low, the fiber smoothness is high and the porosity is high.

[0036] Step 4: Interface bonding between the energy storage unit and the self-powered unit: The energy storage fiber is immersed in liquid metal (gallium-indium alloy) for 2 hours, forming a liquid metal interface on the fiber surface. Based on this, silver-plated nylon yarn is used at 30... o The spiral winding method is combined with energy storage fibers to serve as electrodes for the self-powered unit. The silver-plated nylon yarn has a resistivity of 0.3 Ω / cm, a breaking strength of 15 cN / dtex, and a silver content of 20%.

[0037] Step 5: Prepare spinning solution B for the self-powered unit: Obtain a mixed solvent by mixing N,N-dimethylformamide and acetone at a mass ratio of 3:2. Dissolve P(VDF-TrFE) and BaTiO3 together in this mixed solvent to prepare an 8% P(VDF-TrFE) solution with a mass ratio of P(VDF-TrFE) to BaTiO3 of 5:1, thus obtaining spinning solution B.

[0038] Step 6: Prepare the self-powered unit to obtain the final integrated yarn: Dispense the spinning solution B into two 10ml syringes and fix them. Connect 23G plastic needles to the positive and negative power supplies, with a distance of 15cm between the two needle tips. The electrospinning flow rate is fixed at 0.5ml / h, the positive and negative voltages are 4kV, the disc rotation speed is 700rpm, the collecting shaft speed is 1mm / s, the distance between the needle tip and the disc collector is 4cm, the temperature is 35°C, and the humidity is 40%RH. Place the yarn in an oven at 80°C for 2 hours.

[0039] The final integrated yarn exhibited a specific capacitance of 2.5 F / g, an output voltage of 1.5 V, an output current of 0.8 μA, a breaking strength of 9 MPa, and a sensitivity of 4.53 V / N. Its power generation, energy storage, and sensing performance all met the technical requirements.

[0040] Example 2 This embodiment 2 follows the steps described above, and the specific process is as follows: Preparatory steps and material selection: Same as in Example 1.

[0041] Step 1: Preparation of MXene intermediate: Hydrochloric acid and lithium fluoride were mixed in a 15:1 mass ratio, and lithium fluoride and aluminum carbide were mixed in a 1.5:1 mass ratio in a polytetrafluoroethylene beaker. The three substances were stirred in a water bath at 45°C for 40 hours. The etched solution was centrifuged at 4000 rpm and acid-washed until pH=7. The acid-washed liquid was filtered and dried at 45°C for 18 hours. The resulting solid was sonicated for 2 hours and then centrifuged. The supernatant was freeze-dried at -80°C for 48 hours to obtain the MXene intermediate.

[0042] Step 2: Preparation of spinning solution A for the MXene / TPU / PDA system: TPU was dissolved in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 3:1. The solution was stirred at 60°C for 5 hours under sealed conditions to prepare a 10% TPU solution. Then, MXene intermediate and dopamine hydrochloride at a mass ratio of 100:10 were added to the TPU solution and stirred for 2 hours. The mass ratio of MXene intermediate to TPU was 1:1. The spinning solution was ultrasonicated in an ice-water bath for 2 hours, stirred for 60 minutes, and allowed to stand for 10 hours to obtain spinning solution A.

[0043] Step 3, Preparation of Energy Storage Fiber: 3 ml of spinning solution A is drawn using a 5 ml syringe, and then injected at a rate of 10 ml / h using a micro-injection pump. -1 The spinning solution A was injected into a deionized water coagulation bath using a circular needle (size 21, inner diameter 0.51 mm) at the specified injection rate. After coagulation in the coagulation bath for 25 minutes, the solution was removed and dried at room temperature for 5 hours to complete the preparation of MXene / TPU / PDA fibers.

[0044] Step 4: Interface bonding between the energy storage unit and the self-powered unit: The energy storage fiber is immersed in liquid metal for 2.5 hours to form a liquid metal interface on the fiber surface. Based on this, silver-plated nylon yarn is used at 40... o The spiral winding method is combined with energy storage fibers to serve as electrodes for the self-powered unit. The silver-plated nylon yarn has a resistivity of 0.6 Ω / cm, a breaking strength of 17 cN / dtex, and a silver content of 50%.

[0045] Step 5: Preparation of spinning solution B for the self-powered unit: A mixed solvent is obtained by mixing N,N-dimethylformamide and acetone at a mass ratio of 5:3. P(VDF-TrFE) and BaTiO3 are dissolved together in this mixed solvent to prepare a P(VDF-TrFE) solution with a concentration of 11% and a mass ratio of P(VDF-TrFE) to BaTiO3 of 4:1, thus obtaining spinning solution B.

[0046] Step 6: Prepare the self-powered unit to obtain the final integrated yarn: Dispense the spinning solution B into two 10ml syringes and fix them. Connect the 23G plastic needles to the positive and negative power supplies, with a distance of 15cm between the two needle tips. The electrospinning flow rate is fixed at 0.5ml / h, the positive and negative voltages are 5kV, the disc rotation speed is 500rpm, the collecting shaft speed is 1mm / s, the distance between the needle tip and the disc collector is 4cm, the temperature is 40°C, and the humidity is 40%RH. Place the yarn in a 70°C oven for 2 hours.

[0047] The final integrated yarn has a specific capacitance of 5.2 F / g, an output voltage of 6.5 V, and an output current of 1.2 μA.

[0048] Example 3 This embodiment 3 follows the steps described above, and the specific process is as follows: Preparatory steps, 1) Material selection: Same as in Example 1.

[0049] Step 1: Preparation of MXene intermediate: Hydrochloric acid and lithium fluoride were mixed at a mass ratio of 30:1, and lithium fluoride and aluminum carbide were mixed at a mass ratio of 2:1 in a polytetrafluoroethylene beaker. The three substances were stirred in a water bath at 40°C for 40 h. The etched solution was centrifuged at 4000 rpm and acid-washed until pH=7. The acid-washed liquid was filtered and dried at 42°C for 18 h. The resulting solid was sonicated for 2 h and then centrifuged. The supernatant was freeze-dried at -75°C for 48 h to obtain the MXene intermediate.

[0050] Step 2: Preparation of spinning solution A for the MXene / TPU / PDA system: TPU was dissolved in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 4:1. The solution was stirred at 60°C for 5 hours under sealed conditions to prepare an 11% TPU solution. Then, MXene intermediate and dopamine hydrochloride at a mass ratio of 100:15 were added to the TPU solution and stirred for 2 hours. The mass ratio of MXene intermediate to TPU was 7:3. The spinning solution was ultrasonicated in an ice-water bath for 2 hours, stirred for 60 minutes, and allowed to stand for 10 hours to obtain spinning solution A.

[0051] Step 3, Preparation of Energy Storage Fiber: 3 ml of spinning solution A is drawn using a 5 ml syringe, and then injected at a rate of 12 ml / h using a micro-injection pump. -1 The spinning solution was injected into a deionized water coagulation bath using a circular needle (size 21, inner diameter 0.51 mm) at a specific injection rate. After coagulation for 20 minutes, the fibers were removed and dried at room temperature for 5 hours to complete the preparation of MXene / TPU / PDA fibers. The surface morphology of these fibers is as follows: Figure 5 As shown, when the MXene loading increases, the surface smoothness of the fiber decreases, and MXene nanosheets precipitate.

[0052] Step 4: Interface bonding between the energy storage unit and the self-powered unit: The energy storage fiber is immersed in liquid metal for 3 hours, forming a liquid metal interface on the fiber surface, the surface morphology of which is as follows. Figure 6 As shown, liquid metal forms a dense, uniform thin film on the fiber surface. Based on this, silver-plated nylon yarn is used at 45... o The spiral winding method is combined with energy storage fibers to serve as electrodes for the self-powered unit. The silver-plated nylon yarn has a resistivity of 1 Ω / cm, a breaking strength of 20 cN / dtex, and a silver content of 80%.

[0053] Step 5: Preparation of spinning solution B for the self-powered unit: A mixed solvent is obtained by mixing N,N-dimethylformamide and acetone at a mass ratio of 5:3. P(VDF-TrFE) and BaTiO3 are dissolved together in this mixed solvent to prepare a 14% P(VDF-TrFE) solution with a mass ratio of P(VDF-TrFE) to BaTiO3 of 5:1, thus obtaining spinning solution B.

[0054] Step 6: Prepare the self-powered unit to obtain the final integrated yarn: Dispense the spinning solution B into two 10ml syringes and fix them in place. Connect 23G plastic needles to the positive and negative power supplies, with a distance of 15cm between the two needle tips. The electrospinning flow rate is fixed at 0.7ml / h, the positive and negative voltage is 3.5kV, the disc rotation speed is 500rpm, the collecting shaft speed is 1mm / s, the distance between the needle tip and the disc collector is 4cm, the temperature is 40°C, and the humidity is 50%RH. Place the yarn in a 70°C oven for 2 hours.

[0055] The final integrated yarn exhibited a specific capacitance of 7.5 F / g, an output voltage of 3.2 V, an output current of 1.4 μA, a breaking strength of 8.8 MPa, and a sensitivity of 4.2 V / N. Its power generation, energy storage, and sensing performance all met the technical requirements.

[0056] Example 4 This embodiment 4 follows the steps described above, and the specific process is as follows: Preparatory steps and material selection: Same as in Example 1.

[0057] Step 1: Preparation of MXene intermediate: Hydrochloric acid and lithium fluoride were mixed in a 15:1 mass ratio, and lithium fluoride and aluminum carbide were mixed in a 2:1 mass ratio in a polytetrafluoroethylene beaker. The three substances were stirred in a water bath at 37°C for 35 h. The etched solution was centrifuged at 4000 rpm and acid-washed until pH=7. The acid-washed liquid was filtered and dried at 44°C for 18 h. The resulting solid was sonicated for 2.5 h and then centrifuged. The supernatant was freeze-dried at -78°C for 48 h to obtain the MXene intermediate.

[0058] Step 2: Preparation of spinning solution A for the MXene / TPU / PDA system: TPU was dissolved in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 4:1, and stirred at 60°C for 5 hours under sealed conditions to prepare a 10% TPU solution. Then, MXene intermediate and dopamine hydrochloride at a mass ratio of 100:5 were added to the TPU solution and stirred for 2 hours. The mass ratio of MXene intermediate to TPU was 1:1. The spinning solution was ultrasonicated in an ice-water bath for 2 hours, stirred for 60 minutes, and allowed to stand for 10 hours to obtain spinning solution A.

[0059] Step 3, Preparation of Energy Storage Fiber: Use a 5ml syringe to draw 2ml of spinning solution A, and use a micro-injection pump to dispense 10ml of solution at a rate of 10ml / h. -1 The spinning solution A was injected into a deionized water coagulation bath using a circular needle (size 21, inner diameter 0.51 mm) at the specified injection rate. After coagulation in the coagulation bath for 28 min, the solution was removed and dried at room temperature for 3.5 h to complete the preparation of MXene / TPU / PDA fibers.

[0060] Step 4: Interface bonding between the energy storage unit and the self-powered unit: The energy storage fiber is immersed in liquid metal for 2 hours to form a liquid metal interface on the fiber surface. Based on this, silver-plated nylon yarn is used at 40... o The spiral winding method is combined with energy storage fibers to serve as electrodes for the self-powered unit. The silver-plated nylon yarn has a resistivity of 0.8 Ω / cm, a breaking strength of 18 cN / dtex, and a silver content of 60%.

[0061] Step 5: Preparation of spinning solution B for the self-powered unit: A mixed solvent is obtained by mixing N,N-dimethylformamide and acetone at a mass ratio of 3:2. P(VDF-TrFE) and BaTiO3 are dissolved together in this mixed solvent to prepare a P(VDF-TrFE) solution with a concentration of 11%. The mass ratio of P(VDF-TrFE) to BaTiO3 is 3:1, thus obtaining spinning solution B.

[0062] Step 6: Prepare the self-powered unit to obtain the final integrated yarn: Dispense the spinning solution B into two 10ml syringes and fix them in place. Connect the 23G plastic needles to the positive and negative power supplies, with a distance of 15cm between the two needle tips. The electrospinning flow rate is fixed at 1ml / h, the positive and negative voltages at 5kV, the disc rotation speed at 500rpm, the collecting shaft speed at 1mm / s, the distance between the needle tip and the disc collector at 4cm, the temperature at 40°C, and the humidity at 40%RH. Place the yarn in a 70°C oven for 2 hours.

[0063] The final integrated yarn exhibited a specific capacitance of 12 F / g, an output voltage of 11.9 V, an output current of 1.8 μA, a breaking strength of 9.3 MPa, and a sensitivity of 4.5 V / N.

[0064] Example 5 This embodiment 5 follows the steps described above, and the specific process is as follows: Preparatory steps, 1) Material selection: Same as in Example 1.

[0065] Step 1: Preparation of MXene intermediate: Hydrochloric acid and lithium fluoride were mixed in a 30:1 mass ratio, and lithium fluoride and aluminum carbide were mixed in a 2:1 mass ratio in a polytetrafluoroethylene beaker. The three substances were stirred in a water bath at 40°C for 40 h. The etched solution was centrifuged at 4000 rpm and acid-washed until pH=7. The acid-washed liquid was filtered and dried at 40°C for 18 h. The resulting solid was sonicated for 2 h and then centrifuged. The supernatant was freeze-dried at -78°C for 48 h to obtain the MXene intermediate.

[0066] Step 2: Preparation of spinning solution A for the MXene / TPU / PDA system: TPU was dissolved in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 3:1. The solution was stirred at 60°C for 5 hours under sealed conditions to prepare an 11% TPU solution. Then, MXene intermediate and dopamine hydrochloride at a mass ratio of 100:10 were added to the TPU solution and stirred for 2 hours. The mass ratio of MXene intermediate to TPU was 9:1. The spinning solution was ultrasonicated in an ice-water bath for 2 hours, stirred for 60 minutes, and allowed to stand for 12 hours to obtain spinning solution A.

[0067] Step 3, Preparation of Energy Storage Fiber: 3 ml of spinning solution A is drawn using a 5 ml syringe, and then injected at a rate of 10 ml / h using a micro-injection pump. -1 The spinning solution was injected into a deionized water coagulation bath using a circular needle (size 21, inner diameter 0.51 mm) at the specified injection rate. After coagulation in the coagulation bath for 20 minutes, the solution was removed and dried at room temperature for 3 hours to complete the preparation of MXene / TPU / PDA fibers.

[0068] The above-described energy storage performance tests of MXene and TPU with different mass ratios are as follows: Figure 7a , Figure 7b , Figure 7c As shown, Figure 7a The image shows a comparison of the electrochemical impedance spectroscopy of the fibers. When the mass ratio of MXene to TPU is 7:3, the semicircle in the high-frequency region is the smallest, and the slope in the low-frequency region is the largest, indicating superior ion transport capability. Figure 7b This is a comparison chart of the cyclic voltammetry curves of the fiber, and... Figure 7a Correspondingly, when the mass ratio of MXene to TPU is 7:3, the CV curve encloses the largest area and has the strongest energy storage capacity. Figure 7c The constant current charge-discharge test comparison chart of the fiber shows that when the mass ratio of MXene to TPU is 7:3, the discharge time is the longest, indicating the best specific capacitance performance. Figure 7a and Figure 7b The displayed results correspond to this.

[0069] Step 4: Interface bonding between the energy storage unit and the self-powered unit: The energy storage fiber is immersed in liquid metal for 3 hours to form a liquid metal interface on the fiber surface. Based on this, silver-plated nylon yarn is used at 37... o The spiral winding method is combined with energy storage fibers to serve as electrodes for the self-powered unit. The silver-plated nylon yarn has a resistivity of 1 Ω / cm, a breaking strength of 20 cN / dtex, and a silver content of 80%.

[0070] Step 5: Preparation of spinning solution B for the self-powered unit: A mixed solvent is obtained by mixing N,N-dimethylformamide and acetone at a mass ratio of 5:3. P(VDF-TrFE) and BaTiO3 are dissolved together in this mixed solvent to prepare a 10% P(VDF-TrFE) solution with a mass ratio of P(VDF-TrFE) to BaTiO3 of 5:1, thus obtaining spinning solution B. Figure 11 The power generation performance of P(VDF-TrFE) yarns with different concentrations is shown, with the highest performance at a concentration of 10%.

[0071] Step 6: Prepare the self-powered unit to obtain the final integrated yarn: Dispense the spinning solution B into two 10ml syringes and fix them. Connect 23G plastic needles to the positive and negative power supplies, with a distance of 15cm between the needle tips. The electrospinning flow rate is fixed at 0.7ml / h, the positive and negative voltages at 3.5kV, the disc rotation speed at 500rpm, the collecting shaft speed at 1mm / s, the distance between the needle tip and the disc collector at 4cm, the temperature at 40°C, and the humidity at 50%RH. Place the yarn in a 70°C oven for 2 hours. The surface morphology, cross-sectional morphology, and their magnified images of the integrated yarn are shown below. Figure 8a , Figure 8b As shown. Figure 8a It shows the surface morphology and magnified image of the integrated yarn, revealing the electrospun nanofibers and barium titanate particles. Figure 8b The integrated yarn cross-sectional morphology and magnified image clearly show the silver-plated nylon yarn and energy storage fibers inside the yarn, proving the successful construction of the yarn's asymmetric structure and the integration of the energy storage unit and self-powered unit. Figure 9 The image showcases the process from energy storage fibers to composite fibers combined with silver-plated nylon yarn, and finally, a physical image of the integrated yarn. EDS characterization is shown below. Figure 10a , Figure 10b , Figure 10c As shown in the figure (the main idea to be expressed in the figure is briefly explained). Figure 10a The image shows a comparison of EDS elemental distribution between P(VDF-TrFE) yarn (without integrated energy storage units and barium titanate) and integrated yarn. In contrast, no Ba and Ti elements were detected on the surface of the P(VDF-TrFE) yarn, while Ba and Ti elements were clearly present on the surface of the integrated yarn. Figure 10b and Figure 10c Further quantitative analysis of the elemental content in the two yarns proved that barium titanate had been successfully introduced into the integrated yarn. Figure 12 It is the voltage output of the integrated yarn under different impact frequencies, which is basically stable at 24.8V. As the frequency increases, the stability decreases.

[0072] The final integrated yarn exhibited a specific capacitance of 16.2 F / g, an output voltage of 24.8 V, an output current of 2.4 μA, a breaking strength of 10 MPa, and a sensitivity of 4.8 V / N. Its power generation, energy storage, and sensing performance all met the technical requirements.

[0073] Example 6 This embodiment 5 follows the steps described above, and the specific process is as follows: Preparatory steps, 1) Material selection: Same as in Example 1.

[0074] Step 1: Preparation of MXene intermediate: Hydrochloric acid and lithium fluoride were mixed in a 30:1 mass ratio, and lithium fluoride and aluminum carbide were mixed in a 1:1 mass ratio in a polytetrafluoroethylene beaker. The three substances were stirred in a water bath at 40°C for 31 h. The etched solution was centrifuged at 4000 rpm and acid-washed until pH=7. The acid-washed liquid was filtered and dried at 41°C for 18 h. The resulting solid was sonicated for 2 h and then centrifuged. The supernatant was freeze-dried at -70°C for 48 h to obtain the MXene intermediate.

[0075] Step 2: Preparation of spinning solution A for the MXene / TPU / PDA system: TPU was dissolved in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 4:1. The solution was stirred at 60°C for 5 hours under sealed conditions to prepare a 12% TPU solution. Then, MXene intermediate and dopamine hydrochloride were added to the TPU solution at a mass ratio of 100:5 and stirred for 2 hours. The mass ratio of MXene intermediate to TPU was 7:3. The spinning solution was ultrasonicated in an ice-water bath for 2 hours, stirred for 60 minutes, and allowed to stand for 12 hours to obtain spinning solution A.

[0076] Step 3, Preparation of Energy Storage Fiber: 3 ml of spinning solution A is drawn using a 5 ml syringe, and then injected at a rate of 7 ml / h using a micro-injection pump. -1 The spinning solution was injected into a deionized water coagulation bath using a circular needle (size 21, inner diameter 0.51 mm) at the specified injection rate. After coagulation in the coagulation bath for 30 minutes, the solution was removed and dried at room temperature for 4 hours to complete the preparation of MXene / TPU / PDA fibers.

[0077] Step 4: Interface bonding between the energy storage unit and the self-powered unit: The energy storage fiber is immersed in liquid metal for 2 hours to form a liquid metal interface on the fiber surface. Based on this, silver-plated nylon yarn is used at 40... o The spiral winding method is combined with energy storage fibers to serve as electrodes for the self-powered unit. The silver-plated nylon yarn has a resistivity of 0.9 Ω / cm, a breaking strength of 19 cN / dtex, and a silver content of 70%.

[0078] Step 5: Preparation of spinning solution B for the self-powered unit: A mixed solvent is obtained by mixing N,N-dimethylformamide and acetone at a mass ratio of 3:2. P(VDF-TrFE) and BaTiO3 are dissolved together in this mixed solvent to prepare a 14% P(VDF-TrFE) solution with a mass ratio of 5:1 to obtain spinning solution B.

[0079] Step 6: Prepare the self-powered unit to obtain the final integrated yarn: Dispense the spinning solution B into two 10ml syringes and fix them. Connect the 23G plastic needles to the positive and negative power supplies, with a distance of 15cm between the two needle tips. The electrospinning flow rate is fixed at 0.7ml / h, the positive and negative voltage is 3.5kV, the disc rotation speed is 700rpm, the collecting shaft speed is 1mm / s, the distance between the needle tip and the disc collector is 4cm, the temperature is 35°C, and the humidity is 40%RH. Place the yarn in an oven at 80°C for 2 hours.

[0080] The final integrated yarn exhibited a specific capacitance of 4.2 F / g, an output voltage of 11.3 V, an output current of 1.4 μA, a breaking strength of 8.9 MPa, and a sensitivity of 0.45 V / N. Its power generation, energy storage, and sensing performance all met the technical requirements. Figure 13 It integrates yarn to monitor the electrical signals of different parts of the human body. The signal shape is different depending on the part of the body that is moving, and the human body movement can be identified by the signal shape.

Claims

1. An integrated yarn with asymmetric partitioning that combines power generation, energy storage, and sensing, characterized in that: This includes energy storage fibers prepared using TPU / MXene / PDA, which are impregnated with liquid metal. Silver-plated nylon yarns are spirally wound around the surface of the energy storage fibers, and P(VDF-TrFE) / BaTiO3 is deposited on the surface of the silver-plated nylon yarn winding layer.

2. The integrated yarn with asymmetric partitioning that combines power generation, energy storage, and sensing according to claim 1, characterized in that: In the energy storage fiber, the mass ratio of MXene to PDA is 100: (5~15), and the mass ratio of MXene to TPU is 3:7~9:

1.

3. The integrated yarn with asymmetric partitioning that combines power generation, energy storage, and sensing according to claim 1, characterized in that: The liquid metal is a gallium-indium alloy with a mass ratio of gallium to indium of (2~3):

1.

4. The integrated yarn with asymmetric partitioning that combines power generation, energy storage, and sensing according to claim 1, characterized in that: In the aforementioned P(VDF-TrFE) / BaTiO3, P(VDF-TrFE) represents polyvinylidene fluoride-trifluoroethylene, BaTiO3 represents barium titanate, the concentration of P(VDF-TrFE) solution is 8%-14%, and the mass ratio of P(VDF-TrFE) to BaTiO3 is (3~5):

1.

5. A method for preparing an asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing, characterized in that, Follow these steps: Step 1: Prepare MXene intermediates; Step 2: Prepare spinning solution A for the MXene / TPU / PDA system; Step 3: Prepare energy storage fibers of MXene / TPU / PDA; Step 4: Integrate the interface between the energy storage unit and the self-powered unit; Step 5: Prepare spinning solution B for the self-powered unit; Step 6: Prepare the self-powered unit to finally obtain the integrated yarn.

6. The method for preparing the asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing according to claim 5, characterized in that, In step 1, the specific process is as follows: 1.1) Weigh hydrochloric acid, lithium fluoride, and aluminum carbide together and put them into a beaker made of polytetrafluoroethylene material and mix them. The mass ratio of hydrochloric acid to lithium fluoride is (30~15):1, and the mass ratio of lithium fluoride to aluminum carbide is (1~2):

1. 1.2) The polytetrafluoroethylene beaker containing the above three substances was stirred in a water bath at 35℃~40℃ for 31h~40h. The etched solution was centrifuged and acid-washed at 3500rpm~4000rpm until pH=6~7. The acid-washed liquid was filtered and dried at 40℃~45℃ for 18h~25h. After sonication for 2h~3h, it was centrifuged and the supernatant was freeze-dried at -70℃~-80℃ for 48h~72h to obtain MXene intermediate.

7. The method for preparing the asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing according to claim 5, characterized in that, Step 2, the specific process is as follows: 2.1) Dissolve TPU in a mixed solution of N,N dimethylformamide and tetrahydrofuran at a mass ratio of (4~2):1, and stir at 58℃~63℃ for 5h~6h under sealed conditions to obtain a TPU preparation solution with a concentration of 9%~12%. 2.2) Weigh out MXene intermediate and dopamine hydrochloride in a mass ratio of 100:(5~15) and add them together to the TPU preparation solution. The mass ratio of MXene intermediate to TPU preparation solution is 3:7~9:

1. Stir for 2h~4h to obtain spinning mixture. 2.3) After sonicating the spinning mixture in an ice-water bath for 2-3 hours, stir for 30-60 minutes and let it stand for 7-12 hours to obtain spinning solution A.

8. The method for preparing the asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing according to claim 5, characterized in that, Step 3, the specific process is as follows: Draw 3ml-5ml of spinning solution A with a syringe, and then add it at a rate of 7ml / h. -1 ~12mlh -1 At a certain injection rate, the spinning solution A was injected into a coagulation bath of deionized water and coagulated for 20-30 minutes. After being removed, it was dried at room temperature for 3-5 hours to obtain MXene / TPU / PDA energy storage fiber.

9. The method for preparing the asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing according to claim 5, characterized in that, Step 4, the specific process is as follows: 4.1) The energy storage fiber of MXene / TPU / PDA is immersed in liquid metal for 2h~3h to form a liquid metal interface on the surface of the energy storage fiber, which is called an energy storage unit; the liquid metal is a gallium-indium alloy with a mass ratio of gallium to indium of (2~3):1; 4.2) Use silver-plated nylon yarn at 30 o ~45 o The spiral winding method is combined with the impregnated energy storage fiber, which is called a self-powered unit. The silver-plated nylon yarn serves as the electrode of the self-powered unit.

10. The method for preparing the asymmetric partitioned integrated yarn that combines power generation, energy storage, and sensing according to claim 5, characterized in that, Step 6 involves the following specific steps: The spinning solution B was dispensed into two conjugate spinning needles and secured securely. The plastic needles were connected to the positive and negative power supplies, with the distance between the two needle tips being 12cm to 15cm. Electrospinning was then performed. The electrospinning parameters were as follows: fixed flow rate of 0.5 to 0.55 ml / h, positive and negative voltages of 3.5kV to 5kV, disc rotation speed of 500 rpm to 700 rpm, collecting shaft speed of 1 mm / s to 2 mm / s, distance between the needle tip and the disc collector of 4cm to 6cm, temperature of 35°C to 40°C, and humidity of 40%RH to 50%RH. Then, the yarn prepared by electrospinning is placed in an oven at 70°C~80°C for 2h~3h to obtain an integrated yarn with asymmetric partition structure for power generation, energy storage and sensing.

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