CN109039141B

CN109039141B - Flexible stretchable self-charging device based on carbon fibers, preparation method and system

Info

Publication number: CN109039141B
Application number: CN201810771453.2A
Authority: CN
Inventors: 文震; 孙旭辉; 杨艳琴
Original assignee: Suzhou University; Nantong Textile and Silk Industrial Technology Research Institute
Current assignee: Suzhou University; Nantong Textile and Silk Industrial Technology Research Institute
Priority date: 2018-07-13
Filing date: 2018-07-13
Publication date: 2020-04-21
Anticipated expiration: 2038-07-13
Also published as: CN109039141A

Abstract

The invention provides a flexible stretchable self-charging device based on carbon fibers, a preparation method and a system. This self-charging device includes: the solid super capacitor is composed of two groups of capacitor components with the same structure, the two groups of capacitor components are arranged in parallel, two ends of each group of capacitor components are aligned, each group of capacitor components comprises an active material layer and a solid electrolyte layer wrapped on the periphery of the active material layer, and the active material layer is made of carbon fiber materials; the insulating layer is wrapped on the periphery of the solid-state supercapacitor; the friction nanometer generator is coaxially arranged with the solid-state supercapacitor and the insulating layer, the friction nanometer generator comprises a conducting layer and a friction layer wrapped on the periphery of the conducting layer, the conducting layer is wrapped on the periphery of the insulating layer, and the material is carbon fiber material. The self-charging device is low in material price, non-toxic, pollution-free and good in environmental protection performance, has the flexibility, and can be applied to various different fields, such as weaving the self-charging device into a garment or applying the self-charging device to wearable equipment.

Description

Flexible stretchable self-charging device based on carbon fibers, preparation method and system

Technical Field

The invention relates to the field of nano generators and supercapacitors, in particular to a flexible stretchable self-charging device based on carbon fibers, a preparation method and a system.

Background

With the improvement of the living standard of human beings, intelligent wearable electronic equipment is developing vigorously. These electronic devices still adopt traditional batteries to supply power for them at present, but the battery not only does not possess self-charging ability, and the time of endurance is short moreover, therefore needs frequent change of battery, this has greatly restricted wearable electronic device's practical application effect.

Thus, finding a device that can be self-charging and can continue to supply power becomes an inevitable problem. The friction nano-generator can collect and convert various forms of mechanical energy including compression, vibration, rotation, natural wind energy, water energy, etc. into electrical energy. By virtue of the advantages of light weight, small volume, simple synthesis method and the like, the friction nano-generator is increasingly developed in the field of power supply of wearable equipment. For the friction nano generator, mechanical energy can be converted into electric energy, but the friction nano generator cannot store electric charge per se and needs to be combined with energy storage equipment such as a super capacitor, so that the aim of supplying power to wearable electronic equipment is fulfilled. At present, a supercapacitor and a friction nano generator are combined and used, but the device has many limitations in the energy supply problem of wearable equipment, and the device is generally large in size and inconvenient to power the wearable equipment.

Therefore, it is of great significance to research a self-charging system which has high integration level, simple preparation method, low cost, no pollution, high efficiency and is suitable for wearable equipment to meet application requirements.

Disclosure of Invention

The inventor of the present application found that, in the prior art, a supercapacitor and a friction nanogenerator are reported to be woven into a fabric, but two fiber devices are prepared separately and are simply combined during weaving, which undoubtedly limits the application of the supercapacitor and the friction nanogenerator.

The invention aims to solve the technical problem that a device which combines a super capacitor and a friction nano generator is large in size in the prior art.

The invention also aims to solve the technical problem of low integration level of devices which combine and apply the super capacitor and the friction nano generator in the prior art.

It is a further object of the present invention to provide a novel method for making a device that combines a supercapacitor with a triboelectric nanogenerator.

The invention provides a flexible stretchable self-charging device based on carbon fibers, which comprises:

the solid-state supercapacitor is composed of two groups of capacitor components with the same structure, the two groups of capacitor components are arranged in parallel, two ends of each capacitor component are aligned, each group of capacitor components comprises an active material layer and a solid electrolyte layer wrapped on the periphery of the active material layer, and the active material layer is made of carbon fiber materials;

the insulating layer wraps the periphery of the solid-state supercapacitor;

the friction nano generator is coaxially arranged with the solid-state supercapacitor and the insulating layer and comprises a conducting layer and a friction layer wrapping the periphery of the conducting layer, the conducting layer wraps the periphery of the insulating layer, and the conducting layer is made of carbon fiber materials.

Optionally, the active material layer is a carbon fiber bundle woven by the carbon fiber material;

the solid electrolyte layer is arranged to extend from a first end of the carbon fiber bundle to a second end opposite to the first end, and the second end is exposed to serve as an electrode of the solid-state supercapacitor.

Optionally, the conductive layer is wound around the outer periphery of the insulating layer in a spiral winding manner.

Optionally, one end of the conductive layer serves as an electrode of the triboelectric nanogenerator.

Optionally, the solid state supercapacitor is wound on a stretchable substrate.

Optionally, the insulating layer is made of silicon rubber;

optionally, the material of the friction layer is silicone rubber.

In particular, the invention also provides a preparation method of the flexible and stretchable self-charging device based on the carbon fiber, which comprises the following steps:

providing two groups of carbon fiber materials with the same structure;

respectively immersing the two groups of carbon fiber materials into an electrolyte solution, and drying the electrolyte solution to obtain two groups of capacitor components;

arranging the two groups of capacitor assemblies in parallel and aligning two ends of the two groups of capacitor assemblies to form a solid-state supercapacitor in an assembling mode;

coating a liquid insulating material on the periphery of the solid supercapacitor to form an insulating layer on the periphery of the solid supercapacitor after the liquid insulating material is solidified;

and wrapping a carbon fiber material on the periphery of the insulating layer to form a conductive layer, and coating a friction layer material on the periphery of the conductive layer to form a friction layer.

Optionally, the mass ratio of the carbon fiber material to the electrolyte solution is 1: 1000-2000.

Optionally, the electrolyte solution includes polyvinyl alcohol, phosphoric acid, and deionized water.

In particular, the present invention also provides a flexible, stretchable, self-charging system based on carbon fibres, comprising:

the above-described flexible stretchable self-charging device based on carbon fiber;

and the rectifier bridge is used for converting the alternating current signal output by the friction nano generator into a direct current signal and outputting the direct current signal to the solid-state super capacitor.

Optionally, the self-charging device comprises a plurality of solid state supercapacitors connected in series and a plurality of triboelectric nanogenerators connected in parallel.

Before the present application, the inventor of the present application broken through the thought limitations of those skilled in the art and innovatively integrated the two together, thereby forming a self-charging device with simple structure and small volume.

According to the scheme of the embodiment of the invention, the self-charging device is low in material price, non-toxic, pollution-free and good in environmental protection performance. And because carbon fiber and silicon rubber all can take place the deformation after the reconversion, for example the reconversion after the bending to make this self-charging device have the flexibility characteristic, and twine solid-state ultracapacitor system on can stretch the base, thereby make the device have certain tensile performance, can use in various different fields, for example weave into the clothing with it, or use on wearable equipment.

The self-charging system provided by the invention can be well suitable for wearable power supply equipment. The fiber characteristics of the system make the system more beneficial to weaving ready-made clothes, thereby driving various portable wearable electronic devices and meeting the social demands of increasing development. In addition, the self-charging system has low requirements on equipment from preparation to application and is low in cost. The friction nano generator and the solid-state supercapacitor are simple in working mechanism, free of danger in working process and high in efficiency, industrial popularization is facilitated, and remarkable economic benefits and social benefits are achieved.

The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.

Drawings

Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:

FIG. 1 is a schematic block diagram of a carbon fiber based flexible stretchable self-charging device according to one embodiment of the present invention;

FIG. 2 is a schematic flow diagram of a method of making a carbon fiber based flexible stretchable self-charging device according to one embodiment of the present invention;

FIG. 3 is a schematic flow diagram of a process for making a carbon fiber based flexible stretchable self-charging device according to one embodiment of the present invention;

FIG. 4 is a cyclic voltammogram of a single solid-state supercapacitor prepared according to an embodiment of the present invention at different scan rates (5-100 mv/s);

FIG. 5 is a schematic and schematic diagram of a carbon fiber based flexible stretchable self-charging system according to one embodiment of the present invention;

fig. 6 is a charging curve of a carbon fiber-based flexible stretchable self-charging system and a discharging curve for driving a portable electronic timepiece using the same according to an embodiment of the present invention;

FIG. 7 is a schematic diagram of a plurality of solid-state ultracapacitors connected in series according to one embodiment of the invention;

FIG. 8 is a schematic diagram of multiple triboelectric nanogenerators connected in parallel according to one embodiment of the invention;

FIG. 9 is a graph of constant current (5 μ A) charging and discharging of various numbers of solid-state supercapacitors connected in series according to one embodiment of the invention;

FIG. 10 is the output of open circuit voltage, short circuit current, and short circuit charge for four parallel friction nano-generators at different frequencies of motion (1-2.5Hz) according to one embodiment of the present invention.

Detailed Description

Fig. 1 shows a schematic block diagram of a carbon fiber-based flexible stretchable self-charging device according to an embodiment of the present invention. As shown in fig. 1, the self-charging device 10 includes a solid-state supercapacitor 1, an insulating layer 2, and a triboelectric nanogenerator 3. The solid-state supercapacitor 1 is composed of two groups of capacitor assemblies 11 with the same structure, the two groups of capacitor assemblies 11 are arranged in parallel, two ends of each group of capacitor assemblies 11 are aligned, each group of capacitor assemblies 11 comprises an active material layer 111 and a solid electrolyte layer 112 wrapping the periphery of the active material layer 111, and the active material layer 111 is made of carbon fiber materials. The insulating layer 2 is wrapped on the periphery of the solid-state supercapacitor 1. The material of the insulating layer 2 is selected to be elastically deformable. The friction nano-generator 3 is respectively arranged coaxially with the solid-state supercapacitor 1 and the insulating layer 2, the friction nano-generator 3 comprises a conductive layer 31 and a friction layer 32 wrapping the periphery of the conductive layer 31, the conductive layer 31 wraps the periphery of the insulating layer 2, and the material of the conductive layer is carbon fiber material.

Before the present application, the inventor of the present application broken through the thought limitations of the skilled in the art and innovatively integrated the two together to form a self-charging device 10 with simple structure and small volume by connecting the separate solid-state supercapacitor 1 and the triboelectric nanogenerator 3 together to store the electric energy generated by the triboelectric nanogenerator 3 into the solid-state supercapacitor 1.

Referring to fig. 1, the active material layer 111 is a carbon fiber bundle woven from a carbon fiber material. In one embodiment, the solid-state supercapacitor 1 may be wound on a stretchable substrate. The conductive layer 31 of the friction nanogenerator 3 is also a carbon fiber bundle woven from a carbon fiber material, and the carbon fiber bundle is wound around the outer periphery of the insulating layer 2 in a spiral winding manner. The solid electrolyte layer 112 is arranged to extend from a first end 1111 of the carbon fiber bundle to a second end 1112 opposite to the first end 1111 and to expose the second end 1112 to make the second end 1112 as an electrode of the solid-state supercapacitor 1. One end of the conductive layer 31 of the triboelectric nanogenerator 3 serves as an electrode 33 of the triboelectric nanogenerator 3. In one embodiment, the material of the insulating layer 2 is selected to be silicon rubber. The material of the friction layer 32 is selected to be silicone rubber. The insulating layer 2 can prevent the solid-state supercapacitor 1 and the triboelectric nanogenerator 3 from interfering with each other.

According to the scheme of the embodiment of the invention, the self-charging device 10 is made of low-price materials, is non-toxic and pollution-free, and has good environmental protection performance. And because carbon fiber and silicon rubber can all take place the deformation back reconversion, for example the crooked back reconversion to make this self-charging device 10 have flexible characteristic, and twine solid-state ultracapacitor system 1 on can stretching the base, thereby make the device have certain tensile performance, can use in various different fields, for example weave into the clothing with it, or use on wearable equipment.

The operation mode of the friction nano-generator 3 is a single-electrode mode. When the friction nano-generator 3 is in contact with the skin, the silicon rubber can generate negative charges, and when the skin is separated from the friction nano-generator 3, the electrode 33 of the friction nano-generator 3 can be induced with corresponding positive charges, so that current is generated. When the skin is again in contact, the electrodes 33 of the triboelectric nanogenerator 3 again require opposite charges, thereby generating an opposite current.

Fig. 2 shows a schematic flow diagram of a method of manufacturing a carbon fiber based flexible stretchable self-charging device according to one embodiment of the present invention. Fig. 3 shows a schematic flow diagram of a process for the preparation of a carbon fiber based flexible stretchable self-charging device according to one embodiment of the present invention. As shown in fig. 2 and 3, the method includes:

step S100, providing two groups of carbon fiber materials with the same structure;

step S200, respectively immersing two groups of carbon fiber materials into an electrolyte solution, and drying the electrolyte solution to obtain two groups of capacitor assemblies 11;

step S300, arranging two groups of capacitor assemblies 11 in parallel and aligning two ends of the capacitor assemblies to form a solid-state supercapacitor 1;

step S400, coating a liquid insulating material on the periphery of the solid-state supercapacitor 1 so as to form an insulating layer 2 on the periphery of the solid-state supercapacitor 1 after the liquid insulating material is solidified;

step S500, wrapping a carbon fiber material around the insulating layer 2 to form a conductive layer 31, and coating a friction layer 32 material around the conductive layer 31 to form a friction layer 32, thereby preparing and forming the self-charging device 10.

In step S200, the material of the electrolyte solution includes polyvinyl alcohol, phosphoric acid, and deionized water. And the mass ratio of the carbon fiber material to the electrolyte solution is 1: any ratio of 1000-2000 may be, for example, 1:1000, 1:1200, 1:1500, 1:1800, 1:2000, etc.

In step S400, the liquid insulating material may be, for example, liquid silicone rubber. When the insulating layer 2 is prepared, the solid-state supercapacitor 1 can be vertically suspended, so that the liquid glue naturally falls down by utilizing gravity, and the liquid glue wraps the periphery of the solid-state supercapacitor 1. The silicone rubber thus formed is thin and uniform.

In one particular embodiment, the method of making the self-charging device 10 includes the steps of:

taking two carbon fiber bundles of which the number is about 0.2mg, respectively soaking the two carbon fiber bundles in 0.1mL of electrolyte solution (for example, 1g of polyvinyl alcohol, 1mL of phosphoric acid solution and 9mL of deionized water are mixed and stirred at 85 ℃ until the mixture is clear), after the electrolyte is dried, respectively dripping 0.1mL of electrolyte solution, and after the electrolyte is dried, assembling the two carbon fiber bundles in parallel to obtain a solid super capacitor;

and (3) coating liquid silicon rubber on the surface of the fibrous solid capacitor, and curing to obtain the insulating layer 2.

And tightly and uniformly winding about 25mg of carbon fiber bundles on the surface of the insulating layer 2, then coating liquid silicon rubber on the surface of the carbon fiber bundles, and curing to obtain the friction nano-generator 3.

In another embodiment, the ratio of carbon fiber to electrolyte solution in the process of making the solid-state supercapacitor 1 may be 4 mg: 0.4 ml.

FIG. 4 shows cyclic voltammograms of a single solid-state supercapacitor prepared according to an embodiment of the present invention at different scan rates (5-100 mv/s). As can be seen from fig. 4, the cyclic voltammogram of the solid-state supercapacitor 1 is close to rectangular under the condition of slower scanning speed, and shows good capacitance characteristics. As the sweep rate increases, the cyclic voltammogram gradually deviates from a rectangular shape, showing a larger resistance characteristic.

Fig. 5 shows a schematic principle view of a flexible stretchable self-charging system based on carbon fiber according to an embodiment of the present invention. As shown in fig. 5, the self-charging system includes the self-charging device 10 described above and a rectifier bridge 20. In the circuit, a rectifier bridge 20 is used for converting alternating current output by the friction nano-generator 3 into direct current, and the direct current rectified by the rectifier bridge 20 is charged to the coaxial solid-state super capacitor 1. The state of the solid-state supercapacitor 1 is controlled through the switch, when S1 is closed, the friction nanometer generator 3 charges the supercapacitor, and when S2 is closed, the supercapacitor releases electric quantity to drive the electronic device 30. In one embodiment, the self-charging system may be utilized to drive a portable electronic timepiece. Fig. 6 shows a charging curve of a carbon fiber-based flexible stretchable self-charging system and a discharging curve for driving a portable electronic timepiece using the system according to an embodiment of the present invention. As can be seen from fig. 6, the self-charging system can charge a portable electronic timepiece.

In one embodiment, a plurality of solid state supercapacitors 1 and a plurality of triboelectric nanogenerators 3 may be included in the self-charging system. Fig. 7 shows a schematic diagram of a plurality of solid-state supercapacitors connected in series. Figure 8 shows a schematic of multiple triboelectric nanogenerators in parallel. As shown in fig. 7 and 8, the self-charging system may include a plurality of solid-state supercapacitors 1 connected in series and a plurality of friction nanogenerators 3 connected in parallel.

Fig. 9 shows a constant current (5 μ a) charging and discharging graph of solid-state supercapacitors connected in series with different numbers according to one embodiment of the invention. As can be seen from fig. 9, when the input current is 5 μ a, the overall capacitance value decreases as the number of solid-state supercapacitors 1 connected in series increases, and when four solid-state supercapacitors 1 are connected in series, the system capacitance is about 30 μ F.

FIG. 10 shows the output of open circuit voltage, short circuit current, and short circuit charge for four parallel friction nano-generators at different frequencies of motion (1-2.5Hz), according to one embodiment of the present invention. As can be seen from fig. 10, the open circuit voltage of the four friction nanogenerators 3 after being connected in parallel is kept at about 60V; the output short-circuit current increases along with the increase of the frequency, when the frequency is 1Hz, the peak value of the short-circuit current is 0.2 muA, and when the frequency is increased to 2.5Hz, the short-circuit current can reach 0.6 muA; the output short circuit electricity quantity is almost unchanged under different frequencies and is kept at about 20 nC.

As can be seen from fig. 5 to 10, the carbon fiber-based flexible stretchable self-charging system can realize that the electric energy of the friction nano-generator 3 can be stored in the solid-state supercapacitor 1 and can supply power to the electronic device 30. Meanwhile, as can be seen from the figure, to assemble the friction nano-generator 3 and the solid-state supercapacitor 1 into a working self-charging system, circuit design and management are required. The present invention provides the above circuit design and management means, thereby making it possible for the self-charging system to operate. In addition, it is also necessary to reasonably match the output of the friction nanogenerator 3 and the input of the solid-state supercapacitor 1 by connecting different numbers of structural units (the friction nanogenerator 3 and the solid-state supercapacitor 1) in series and parallel in combination with factors such as the motion frequency of the actual situation.

The self-charging system provided by the invention can be well suitable for wearable power supply equipment. The fibrous nature of this system makes it more conducive to knitting ready-to-wear garments, thereby driving a variety of portable wearable electronic devices 30, meeting the ever-growing social needs. In addition, the self-charging system has low requirements on equipment from preparation to application and is low in cost. The friction nano generator 3 and the solid-state super capacitor 1 have simple working mechanism, no danger in the working process and high efficiency, are beneficial to industrial popularization and have obvious economic and social benefits.

Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.

Claims

1. A flexible, stretchable, self-charging device based on carbon fibers, comprising:

the insulating layer wraps the periphery of the solid-state supercapacitor;

2. A flexible, stretchable, self-charging device based on carbon fibers according to claim 1, characterized in that the active material layer is a carbon fiber bundle woven from the carbon fiber material;

3. The carbon fiber-based flexible stretchable self-charging device according to claim 1, wherein the conductive layer is wound around the outer circumference of the insulating layer in a spiral winding manner.

4. A flexible, stretchable, self-charging device based on carbon fibers according to claim 3, characterized in that one end of the conductive layer acts as an electrode of the triboelectric nanogenerator.

5. A flexible, stretchable, self-charging device based on carbon fibers according to claim 3, characterized in that the solid state supercapacitor is wound on a stretchable substrate.

6. Flexible, stretchable, self-charging device based on carbon fibers according to any of claims 1-5, characterized in that the material of the insulating layer is silicone rubber.

7. A flexible, stretchable self-charging device based on carbon fibers according to any of claims 1-5, characterized in that the material of the friction layer is silicone rubber.

8. A method for preparing a carbon fiber-based flexible stretchable self-charging device, for preparing a carbon fiber-based flexible stretchable self-charging device according to any one of claims 1 to 7, comprising the steps of:

providing two groups of carbon fiber materials with the same structure;

9. The production method according to claim 8, wherein the mass ratio of the carbon fiber material to the electrolyte solution is 1: 1000-2000.

10. The method of claim 9, wherein the electrolyte solution comprises polyvinyl alcohol, phosphoric acid, and deionized water.

11. A carbon fiber based flexible stretchable self-charging system comprising:

the carbon fiber-based flexible stretchable self-charging device according to any one of claims 1 to 7;

12. The flexible stretchable self-charging system according to claim 11, wherein the self-charging device comprises a plurality of solid state supercapacitors connected in series and a plurality of triboelectric nanogenerators connected in parallel.