CN113718397B - Fabrication method and application of a fabric-based wearable composite energy harvesting device - Google Patents

Abstract

The invention belongs to the technical field of flexible wearable electronic equipment, and particularly relates to a manufacturing method and application of a fabric-based wearable composite energy collecting device. The device of the invention has lower manufacturing cost and simple manufacturing method; the device has flexibility, bendability, stretchability, good air permeability and comfortable wearing; the wearable device can be continuously powered under the conditions of human body movement and sweating, and can be applied to preparation of wearable electronic products.

Description

Fabrication method and application of a fabric-based wearable composite energy harvesting device

technical field

The invention belongs to the technical field of flexible wearable electronic devices, and in particular relates to a fabric-based wearable composite energy harvesting device and its application.

Background technique

E-textile is the integration of multifunctional electronic products into fashion clothing, which provides new ideas for the further development of wearable electronic products. Among them, the power supply is the basis and core of realizing such multifunctional electronic textiles. However, traditional bulky batteries that power fabrics suffer from deficiencies in flexibility, comfort, light weight and maintenance-free. In view of these deficiencies, the existing solutions are generally to integrate fiber power generation equipment and energy storage equipment into a piece of textiles to build a self-charging power system to provide sustainable power for these electronic products.

Currently, among numerous power generation devices, triboelectric nanogenerators (TENGs) have been proven to be an effective technology for harvesting low-frequency human motion energy. Because TENG has the advantages of simple structure, wide selection of materials, low cost, etc., and it is easy to design into textile fabrics.

At the same time, it is worth noting that human sweat is also a source of energy, because there is a large amount of organic lactic acid in sweat, and lactic acid can be used as a raw material for biofuel cells to generate electricity. At present, the existing biofuel cells mainly use a serpentine structure for the design of the external structure. Since the elastic substrate of this structure is usually waterproof, it may bring uncomfortable and airtight wearing experience to people. Fiber-based biofuel cells can be integrated into multifunctional textiles through stitching or weaving techniques without compromising the stretchability and breathability of the device. Based on this, it is necessary to develop a fabric-based composite energy harvesting device that is comfortable to wear and can simultaneously collect human exercise energy and sweat bioenergy.

SUMMARY OF THE INVENTION

In order to overcome the above-mentioned deficiencies of the prior art, the present invention proposes a fabric-based wearable composite energy harvesting device, which can last for wearable devices under the condition of human movement and sweating Power supply can be applied to the preparation of wearable electronic products.

In order to achieve the above object, the technical scheme adopted in the present invention is:

The present invention provides a fabric-based wearable composite energy harvesting device, the fabric-based wearable composite energy harvesting device includes a fabric-based triboelectric nanogenerator and a fiber-based lactase biofuel cell, and the fabric-based triboelectric nanogenerator Machine and fiber-based lactase biofuel cells are assembled together by stitching, and the fabric-based triboelectric nanogenerator is woven from power-generating fibers, the power-generating fibers include warp power-generating fibers and weft power-generating fibers, and the warp power-generating fibers The fibers and the weft power generating fibers are arranged vertically and crosswise.

Preferably, the power generating fiber is a concentric structure of conductive fiber/fabric/flexible polymer, and the conductive fibers are exposed at both ends. That is, the power generation fiber is a cylindrical structure, which sequentially includes conductive fibers, fabrics and flexible polymers from the inside to the outside.

Preferably, the fiber-based lactase biofuel cell comprises a lactase/conductive fiber-based anode and a reduced oxygen noble metal/conductive fiber-based cathode, the lactase/conductive fiber-based anode and the reduced oxygen noble metal/conductive fiber-based cathode Cross stitching is fixed on the surface of the fabric-based triboelectric nanogenerator, the lactic enzyme/conductive fiber-based anode and the reducing oxygen noble metal/conductive fiber-based cathode are arranged in parallel, and the stitching direction is consistent.

Preferably, for the power-generating fibers and the lactase/conductive fiber-based anode and the oxygen-reducing noble metal/conductive fiber-based cathode, the conductive fibers include carbon fibers, graphene fibers, and carbon nanotube fibers. In addition, the conductive fibers can also be replaced with conductive wires such as gold, silver, copper, nickel, platinum wires, and the like.

Preferably, the flexible polymer comprises Ecolfelx, polydimethylsiloxane (PDMS), polyurethane, SEBS (hydrogenated styrene-butadiene block copolymer).

The invention integrates a fiber-based biofuel cell and a fabric-based wearable triboelectric nanogenerator, and designs a fabric-based composite energy collection device that can simultaneously collect human exercise energy and sweat bioenergy, and the wearable device can be continuously powered and can be Applied to the preparation of wearable electronic products.

Preferably, the fabric includes cotton thread, wool yarn, silk, acrylic, polyester, nylon.

Preferably, the weaving process of the fabric-based triboelectric nanogenerator includes weaving process, bar knitting process, and crochet knitting process. Further, the weaving process of the fabric-based triboelectric nanogenerator adopts a weaving process.

Preferably, the lactate enzymes include lactate oxidase and lactate dehydrogenase.

Preferably, the oxygen-reducing noble metal includes Pt, Pd, Ru or oxides thereof.

Preferably, in the process of weaving the fabric-based triboelectric nanogenerator, by reasonably arranging the density of warp and weft threads and replacing different weft thread materials, different modes of triboelectric nanogenerators can be obtained, that is, the triboelectric nanogenerator is not limited to the single-electrode mode , and can also manufacture two-electrode mode and free-motion mode.

The present invention also provides a method for preparing the above-mentioned fabric-based wearable composite energy harvesting device, which comprises the following steps:

S1. The conductive fibers are tightly wound and wrapped with a fabric in the circumferential direction of the conductive fibers, and some conductive fibers are exposed at both ends to obtain the conductive fibers wrapped by the fabric;

S2, configure a flexible polymer solution;

S3, soaking the fabric-wrapped conductive fiber of step S1 in the flexible polymer solution of step S2, taking out and removing excess flexible polymer solution, and drying at 70-90° C. for 1-3 hours to obtain power-generating fibers;

S4, firstly arranging the power-generating fibers in step S3 along the warp direction by using the weaving process, then arranging the remaining length power-generating fibers along the weft direction, and weaving to obtain a fabric-based triboelectric nanogenerator that is vertically cross-arranged in the warp and weft directions;

S5, sequentially impregnating conductive fibers with naphthoquinone solution, lactate oxidase and chitosan/glutaraldehyde mixed solution, and drying to obtain lactase/conductive fiber-based anode;

S6, impregnating the conductive fibers with the mixed solution of the reduced oxygen precious metal and the conductive fiber, and drying to obtain the reduced oxygen precious metal/conductive fiber-based cathode;

S7, the lactic enzyme/conductive fiber-based anode of step S5 and the reduced oxygen noble metal/conductive fiber-based cathode of step S6 are respectively sewed on the surface of the fabric-based triboelectric nanogenerator to prepare a fabric-based wearable composite energy harvesting device .

Preferably, the preparation method of the naphthoquinone (NQ) solution is as follows: 0.065 g of naphthoquinone is dissolved in 2 mL of anhydrous ethanol, stirred for 2 hours and then left to stand, and the supernatant is obtained.

Preferably, the lactate oxidase (LOx) solution is prepared by dissolving 25 mg of LOx enzyme in 417 μL of 0.01 M PBS solution, and adding 6.25 mg of BSA (bovine serum albumin) to ensure the activity of the enzyme.

Preferably, the configuration method of the chitosan/glutaraldehyde mixed solution is as follows: mixing 1% chitosan solution and 1% glutaraldehyde solution.

Preferably, the configuration method of the mixed solution of the reduced oxygen noble metal and the conductive fiber: weigh 40 mg of the reduced oxygen noble metal oxide powder and 20 mg of the conductive fiber powder, and dissolve them in 2 mL of Nafion solution with a concentration of 1%.

The present invention also provides the application of the above-mentioned fabric-based wearable composite energy harvesting device in the preparation of wearable electronic products.

Compared with the prior art, the beneficial effects of the present invention are:

The fabric-based wearable composite energy harvesting device provided by the present invention includes a fabric-based triboelectric nanogenerator and a fiber-based lactase biofuel cell, which are assembled together by stitching The fabric-based triboelectric nanogenerator is woven from power generation fibers, the power generation fibers include warp power generation fibers and weft power generation fibers, and the warp power generation fibers and weft power generation fibers are vertically crossed. The invention has the following advantages: (1) the fabrication cost of the device is low, and the fabrication method is simple; (2) the device has flexibility, bendability, stretchability, good air permeability, and is comfortable to wear; (3) the device is woven with textiles , which can supply power to wearable electronic devices in real time; (4) the device can still maintain high output in the case of human sweating.

Description of drawings

Figure 1 is a structural diagram of a fabric-based wearable composite energy harvesting device;

In Figure 1, 1- warp power generation fiber, 2- weft power generation fiber, 3-conductive fiber, 4-lactate oxidase/carbon nanotube fiber-based anode, 5-silver/carbon nanotube fiber-based cathode.

Figure 2 is a schematic cross-sectional view of a power generation fiber;

In Figure 2, 11 - carbon fiber, 12 - cotton thread, 13 - Ecofelx flexible polymer.

Fig. 3 is the output voltage of the fabric-based triboelectric nanogenerator of Example 1;

Fig. 4 is the output current of the fabric-based triboelectric nanogenerator of Example 1;

5 is the output power of the fiber-based lactase biofuel cell of Example 1.

Detailed ways

The specific embodiments of the present invention will be further described below. It should be noted here that the descriptions of these embodiments are used to help the understanding of the present invention, but do not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples can be purchased through conventional commercial channels unless otherwise specified.

Embodiment 1 A kind of fabric-based wearable composite energy harvesting device manufacturing method

As shown in Figures 1 and 2, the fabric-based wearable composite energy harvesting device is assembled by stitching a fabric-based triboelectric nanogenerator and a fiber-based lactase biofuel cell. The fabric-based triboelectric nanogenerator is composed of power generation The fibers are woven by weaving process, and the power generation fibers include warp power generation fibers 1 and weft power generation fibers 2, and the warp power generation fibers 1 and weft power generation fibers 2 are vertically crossed, wherein the power generation fibers It is a concentric structure of carbon fiber 11/cotton thread 12/Ecofelx flexible polymer 13 (that is, it includes carbon fiber 11, cotton thread 12 and Ecofelx flexible polymer 13 in turn from inside to outside), and carbon fibers 11 are exposed at both ends, that is, the cotton thread covered by Ecofelx Wrapped in carbon fiber. The fiber-based lactase biofuel cell includes a lactate oxidase/carbon nanotube fiber-based anode 4 and a silver/carbon nanotube fiber-based cathode 5, the lactate oxidase/carbon nanotube fiber-based anode 4 and silver/carbon nanotube fiber-based anode 4. The tube fiber-based cathode 5 is fixed on the surface of the fabric-based triboelectric nanogenerator by cross-stitching, and the lactate oxidase/carbon nanotube fiber-based anode 4 and the silver/carbon nanotube fiber-based cathode 5 are arranged in parallel and stitched together. In the same direction, the combination of the lactate oxidase/carbon nanotube fiber-based anode 4 and the silver/carbon nanotube fiber-based cathode 5 is provided in three groups in total.

The manufacturing method of the above-mentioned fabric-based wearable composite energy harvesting device comprises the following steps:

(1) Take the carbon fiber 11 with a length of 1.2 m and a diameter of 1 mm, and tightly wrap the cotton thread 12 in the circumferential direction of the carbon fiber 11 until the carbon fiber 11 is completely wrapped, and only the carbon fibers 11 are exposed at both ends to obtain a carbon fiber wrapped by the cotton thread.

(2) Mix the Ecofelx@A bottle with the Ecofelx@B (purchased from Tiantong Huayi, an authorized distributor of Smooth On, USA) in a ratio of 1:1 to obtain an Ecofelx mixed solution.

(3) Immerse the carbon fiber wrapped with cotton thread in Ecofelx mixed liquid for 1 min, then take out the vertical suspension for 5 min, remove the excess Ecofelx mixed liquid, and place the cotton wrapped carbon fiber wrapped with Ecofelx in an oven at 80°C for 2 hours, A length of 1 m and a diameter of about 4 mm were obtained with an Ecofelx-coated cotton-wrapped carbon fiber, that is, a power-generating fiber.

(4) Fabric-based triboelectric nanogenerators are woven from the power-generating fibers by the traditional weaving process. First, the power generation fibers are arranged in parallel along the warp direction into 5 rows, each row is 5cm long, and then the remaining length of the power generation fibers is arranged horizontally along the weft direction by the shuttle (that is, the power generation fibers in the weft direction and the power generation fibers in the warp direction are vertically crossed) , each row is 4 cm long, until the warp is filled with the weft, and weaving to obtain a fabric-based triboelectric nanogenerator that is vertically crossed in the warp and weft directions.

(5) Take carbon nanotube fibers (CNTs) with a length of 2 cm and a diameter of 80 μm, send them to a P15 plasma cleaner for 5 min, and immerse them in a 0.2M NQ solution (preparation method: 0.065g NQ solution) In 2mL of absolute ethanol, stir for 2h, let stand, take the supernatant) for 5min, take it out to dry naturally, repeat 3 times. Then, the carbon nanotube fibers were immersed in 60 mg/mL lactate oxidase (LOx) solution (configuration method: 25 mg LOx enzyme was dissolved in 417 μL 0.01 M PBS solution, and 6.25 mg BSA was added to ensure the activity of the enzyme) for 5 min. After taking out, let it dry naturally at 4°C and repeat 3 times. Finally, the carbon nanotube fibers were immersed in the chitosan/glutaraldehyde mixed solution (preparation method: mix equal volumes of 1% chitosan solution and 1% glutaraldehyde solution) for 5 minutes, take it out to dry naturally, and repeat 3 times, the lactate oxidase/carbon nanotube fiber-based anode 4 was prepared.

(6) Take carbon nanotube fibers with a length of 2 cm and a diameter of 80 μm, send them into a P15 plasma cleaning machine for 5 min, and immerse them in a silver/carbon nanotube mixed solution after taking them out (configuration method: weigh 40 mg Ag ₂ O The powder and 20 mg of CNT powder were dissolved in 2 mL of 1% Nafion solution for 5 min, taken out to dry, and repeated 3 times to obtain a silver/carbon nanotube fiber-based cathode 5.

(7) The lactate oxidase/carbon nanotube fiber-based anode 4 and the silver/carbon nanotube fiber-based cathode 5 are respectively sewed on the surface of the fabric-based triboelectric nanogenerator, and the cathode and anode are sewed in parallel in the meridian direction to prepare the fabric-based Wearable composite energy harvesting device.

Embodiment 2 A kind of fabric-based wearable composite energy harvesting device manufacturing method

The fabric-based wearable composite energy harvesting device is assembled by stitching a fabric-based triboelectric nanogenerator and a fiber-based lactase biofuel cell, and the fabric-based triboelectric nanogenerator is woven from power-generating fibers, and the power-generating fibers Including warp power generation fibers and weft power generation fibers, the warp power generation fibers and weft power generation fibers are vertically crossed, wherein the power generation fibers are carbon fiber/cotton thread/PDMS flexible polymer. The carbon fiber is exposed, that is, the PDMS-coated cotton thread wraps the carbon fiber. The fiber-based lactase biofuel cell includes a lactate oxidase/carbon nanotube fiber-based anode and a silver/carbon nanotube fiber-based cathode, the lactate oxidase/carbon nanotube fiber-based anode and a silver/carbon nanotube fiber-based anode The cathode is fixed on the surface of the fabric-based triboelectric nanogenerator by cross-stitching, the lactate oxidase/carbon nanotube fiber-based anode and the silver/carbon nanotube fiber-based cathode are arranged in parallel, and the stitching direction is consistent, and the lactic acid oxidase/carbon nanotube fiber-based anode is arranged in parallel. The combination of oxidase/carbon nanotube fiber-based anode and silver/carbon nanotube fiber-based cathode is set in three groups in total.

The preparation method of the composite energy harvesting device of this embodiment is basically the same as that of Embodiment 1, and the difference is:

Step (2): In this embodiment, the PDMS base liquid and the curing agent are uniformly mixed in a ratio of 10:1 to obtain a PDMS mixed solution.

Step (3): In this example, the carbon fiber wrapped with cotton thread is immersed in the PDMS mixed liquid for 1 min, then suspended vertically for 5 min, the excess PDMS mixed liquid is removed, and the cotton wrapped carbon fiber wrapped with PDMS is placed in an oven at 80° C. After 2 hours, a PDMS-coated cotton thread-wrapped carbon fiber with a length of 1 m and a diameter of about 4 mm was obtained, that is, a power generation fiber.

Experimental Example 1 Electrical Performance Test

Taking the fabric-based wearable composite energy harvesting device prepared in Example 1 as an example, the exposed carbon fiber end of the power generation fiber was connected to an electrometer [Keithley 6514, KEITHLEY, Tektronix Technology (China) Co., Ltd. The nanogenerator applies a certain frequency and pressure, and the generated electrical signal is captured by the electrometer and the acquisition card, and then transmitted to the computer through the cable to obtain the open-circuit voltage and short-circuit current signals. It can be seen from Figure 3 and Figure 4 that the triboelectric nanogenerator can output a voltage of 140V and a current of 1.95μA.

The above-mentioned fabric-based wearable composite energy harvesting device was attached to the human skin, and one end of the positive and negative wires of the power generation fiber was connected to the negative and positive electrodes of the enzyme biofuel cell, and the other end was connected to an electrochemical workstation (MAC90304, Metrohm, Metrohm, Switzerland). China Co., Ltd.), in the case of human movement and sweating, the enzyme biofuel cell is completely immersed in sweat, causing an electrochemical reaction, and the power density of the enzyme biofuel cell was measured by linear sweep voltammetry versus open circuit voltage. curve. It can be seen from Fig. 5 that the power generated by the enzymatic biofuel cell is 110.5mW·cm ^-3 and the voltage is 0.40V.

To sum up, it can be seen that the electrical energy collected by the triboelectric nanogenerator and the enzymatic biofuel cell of the above-mentioned fabric-based wearable composite energy harvesting device are stored in the corresponding capacitors respectively, and then recombined by the rectifier, which can supply power to small electronic devices.

The embodiments of the present invention have been described above in detail, but the present invention is not limited to the described embodiments. For those skilled in the art, without departing from the principle and spirit of the present invention, various changes, modifications, substitutions and alterations to these embodiments still fall within the protection scope of the present invention.

Claims (7)

1. A fabric-based wearable composite energy harvesting device is characterized in that, the fabric-based wearable composite energy harvesting device comprises a fabric-based triboelectric nanogenerator and a fiber-based lactase biofuel cell, and the fabric-based friction The nanogenerator and the fiber-based lactase biofuel cell are assembled together by stitching, and the fabric-based triboelectric nanogenerator is woven from a power-generating yarn, and the power-generating yarn includes a warp power-generating yarn and a weft power-generating yarn , the warp power generation yarn and the weft power generation yarn are vertically crossed; the power generation yarn is a concentric structure of conductive fiber/cotton thread/flexible polymer, and conductive fibers are exposed at both ends, and the power generation yarn The thread has a cylindrical structure, and includes conductive fibers, cotton threads and flexible polymers in sequence from the inside to the outside. The power-generating yarn is first wrapped around the conductive fibers tightly with the cotton threads, and then the flexible polymer is covered on the conductive fibers wrapped by the cotton threads. The fiber-based lactase biofuel cell includes a lactic enzyme/conductive fiber-based anode and a reduced oxygen noble metal/conductive fiber-based cathode, and the lactic enzyme/conductive fiber-based anode and the reduced oxygen noble metal/conductive fiber-based cathode are The cross stitching is fixed on the surface of the fabric-based triboelectric nanogenerator, the lactic enzyme/conductive fiber-based anode and the reduced oxygen noble metal/conductive fiber-based cathode are arranged in parallel, and the stitching direction is consistent, and the reduced oxygen noble metal includes Pt, Pd, Ru or oxides thereof. 2 . The fabric-based wearable composite energy harvesting device according to claim 1 , wherein the conductive fibers comprise carbon fibers, graphene fibers, and carbon nanotube fibers. 3 . 3 . The fabric-based wearable composite energy harvesting device according to claim 1 , wherein the flexible polymer comprises Ecolfelx, polydimethylsiloxane, polyurethane, and SEBS. 4 . 4 . The fabric-based wearable composite energy harvesting device according to claim 1 , wherein the cotton thread is replaced by any one of wool yarn, silk, acrylic, polyester, and nylon. 5 . 5 . The fabric-based wearable composite energy harvesting device according to claim 1 , wherein the lactate enzyme comprises lactate oxidase and lactate dehydrogenase. 6 . 6. Application of the fabric-based wearable composite energy harvesting device according to any one of claims 1-5 in the preparation of wearable electronic products. 7. The preparation method of the fabric-based wearable composite energy harvesting device according to any one of claims 1-5, characterized in that, comprising the following steps: S1. The conductive fibers are tightly wound and wrapped with cotton threads in the circumferential direction of the conductive fibers, and some conductive fibers are exposed at both ends to obtain the conductive fibers wrapped by the cotton threads; S2, configure a flexible polymer solution; S3, soak the conductive fiber wrapped with the cotton thread in step S1 in the flexible polymer solution of step S2, take out and remove the excess flexible polymer solution, and place it to dry at 70-90° C. for 1-3 hours to obtain a power-generating yarn; S4, firstly arranging the power-generating yarns in step S3 along the warp direction by using the weaving process, then arranging the remaining length power-generating yarns along the weft direction, and weaving to obtain the fabric-based triboelectric nanogenerators that are vertically cross-arranged in the warp and weft directions; S5, sequentially impregnating conductive fibers with naphthoquinone solution, lactate oxidase and chitosan/glutaraldehyde mixed solution, and drying to obtain lactase/conductive fiber-based anode; S6, impregnating the conductive fibers with the mixed solution of the reduced oxygen precious metal and the conductive fiber, and drying to obtain the reduced oxygen precious metal/conductive fiber-based cathode; S7, the lactic enzyme/conductive fiber-based anode of step S5 and the reduced oxygen noble metal/conductive fiber-based cathode of step S6 are respectively sewed on the surface of the fabric-based triboelectric nanogenerator to prepare a fabric-based wearable composite energy harvesting device .

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