阅读说明：本技术 一种压电化学纤维、其制备方法及应用 (Piezoelectric chemical fiber, preparation method and application thereof ) 是由 邸江涛 乔健 靳凯云 李清文 王晓娜 于 2020-04-03 设计创作，主要内容包括：本发明公开了一种压电化学纤维、其制备方法及应用。所述压电化学纤维包括由导电纤维形成的可拉伸结构,且所述可拉伸结构表面覆盖有凝胶电解质；所述压电化学纤维在被施加机械刺激时,两端会产生电势差,从而能够输出电压信号。所述制备方法包括：提供具有大比表面积、可拉伸变形的导电纤维；使凝胶电解质与所述导电纤维的表面接触,获得压电化学纤维,所述压电化学纤维在被施加机械刺激时,两端会产生电势差,从而能够输出电压信号。本发明制备过程简单,直接在大比表面积导电纤维表面涂覆一层凝胶电解质即可实现,且为单电极体系,经过简单封装后即可实现各种环境下的应用,可应用于制备柔性纳米发电机或自供能传感器等领域。(The invention discloses a piezoelectric chemical fiber, a preparation method and application thereof. The piezoelectric chemical fiber comprises a stretchable structure formed by conductive fibers, and the surface of the stretchable structure is covered with gel electrolyte; when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between two ends, so that a voltage signal can be output. The preparation method comprises the following steps: providing a conductive fiber having a large specific surface area and being drawably deformable; and contacting a gel electrolyte with the surface of the conductive fiber to obtain the piezoelectric chemical fiber, wherein when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between the two ends of the piezoelectric chemical fiber, so that a voltage signal can be output. The preparation method is simple in preparation process, can be realized by directly coating a layer of gel electrolyte on the surface of the conductive fiber with large specific surface area, is a single electrode system, can realize application in various environments after simple packaging, and can be applied to the fields of preparing flexible nano generators or self-powered sensors and the like.)

1. A piezoelectric chemical fiber characterized by comprising a stretchable structure formed of a conductive fiber, and the surface of the stretchable structure is covered with a gel electrolyte; when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between two ends, so that a voltage signal can be output.

2. The piezo-chemical fiber of claim 1, wherein: the stretchable structure is formed of elastic conductive fibers.

3. The piezo-chemical fiber of claim 1, wherein: the stretchable structure includes a single helix, a double helix, or a multiple helix structure formed from conductive fibers.

4. A piezo-chemical fiber according to claim 3, wherein: the stretchable structure includes a spiral structure formed by twisting conductive fibers in a stretched state.

5. A piezo-chemical fiber according to claim 3, wherein: the stretchable structure includes a double-spiral structure formed by self-twisting conductive fibers having a single-spiral structure formed by twisting the conductive fibers in a stretched state.

6. The piezo-chemical fiber of claim 1, wherein: the stretchable structure comprises a spring structure formed of conductive fibers.

7. The piezo-chemical fiber of claim 1, wherein: the mechanical stimulus comprises any one or combination of more of asymmetric stretching, twisting and bending.

8. The piezo-chemical fiber of claim 1, wherein: the specific surface area of the piezoelectric chemical fiber is more than 100m²The mechanical strength is more than 150 MPa.

9. The piezo-chemical fiber of claim 1, wherein: the conductive fiber comprises any one or the combination of more than two of carbon nanotube fiber, graphene fiber, conductive polymer fiber and carbon material/polymer composite fiber.

10. A method for preparing a piezoelectric chemical fiber, comprising:

providing a conductive fiber having a large specific surface area and being drawably deformable;

and contacting a gel electrolyte with the surface of the conductive fiber to obtain the piezoelectric chemical fiber, wherein when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between the two ends of the piezoelectric chemical fiber, so that a voltage signal can be output.

11. The method of manufacturing according to claim 10, wherein: the conductive fibers are capable of forming a stretchable structure; and/or the specific surface area of the conductive fiber is more than 100m²A/g, preferably greater than 120m²(iv)/g, tensile strength greater than 150 MPa.

12. The method of manufacturing according to claim 10, wherein: the stretchable structure includes a single helix, a double helix, or a multiple helix structure formed from conductive fibers.

13. The method of manufacturing according to claim 10, wherein: the conductive fiber comprises elastic conductive fiber or inelastic conductive fiber, preferably comprises any one or the combination of more than two of carbon nanotube fiber, graphene fiber, conductive polymer fiber and carbon material/polymer composite fiber.

14. The method according to claim 12, characterized by comprising: and twisting the conductive fiber in a stretching state to obtain the spiral conductive fiber.

15. The method of claim 14, wherein: the speed adopted by the twisting treatment is 60-300 r/min; and/or the twist of the spiral conductive fiber is 15000-30000 r/m.

16. The method of claim 14, further comprising: and self-stranding the spiral conductive fiber to form the double-spiral conductive fiber.

17. The piezo-chemical fiber of claim 11, wherein: the stretchable structure comprises a spring structure formed of conductive fibers.

18. The production method according to claim 1 or 10, characterized by comprising: coating and wrapping the surface of the stretchable structure with gel electrolyte to obtain the piezoelectric chemical fiber.

19. The method of claim 18, wherein: the gel electrolyte comprises a PVA-based gel electrolyte, wherein the electrolyte comprises an acid, base, or chloride salt; preferably, the acid comprises H₂SO₄The base comprises KOH and the salt comprises a chloride salt.

20. The method of manufacturing according to claim 10, wherein: the mechanical stimulus comprises any one or combination of more of asymmetric stretching, twisting and bending.

21. A piezo-chemical fibre produced by the method of any one of claims 10 to 20.

22. Use of a piezo-chemical fibre according to any of claims 1-9, 21 for the manufacture of a flexible nano-generator or a self-powered sensor.

23. An energy conversion mechanism comprising a piezo-chemical fibre according to any one of claims 1 to 9 and 21.

24. The energy conversion mechanism of claim 23, wherein: two ends of the piezoelectric chemical fiber are also respectively connected with electrodes; and/or two ends of the stretchable structure are respectively connected with an electrode in an insulating and sealing manner.

25. A method of converting energy, comprising:

providing a piezo-chemical fiber of any one of claims 1-9, 21; and

and applying mechanical stimulation to the piezoelectric chemical fiber to generate a potential difference at two ends of the piezoelectric chemical fiber and output a voltage signal to realize conversion from mechanical energy to electric energy.

Technical Field

The invention relates to a piezoelectric chemical fiber, in particular to a novel piezoelectric chemical fiber, a preparation method and application thereof, belonging to the technical field of new nano materials.

Background

As a basis for the development and progress of human society, energy is closely related to each of natural and social activities. Over thousands of years of research, energy has been collected and applied to a variety of environments, and a series of energy conversion devices have been developed according to different types and usage forms of energy. Conventional energy harvesting and conversion strategies are typically based on electromagnetic conversion, photovoltaics, thermoelectricity, etc., enabling the conversion of chemical, thermal, mechanical energy into electrical energy. However, with the exhaustion of traditional fossil energy and its environmental pollution, scientists are more inclined to find and utilize new renewable clean energy based on electromechanical conversion rather than chemical-electric and thermal-electric modes.

As is well known, mechanical energy can be converted to electrical energy by electromagnetic induction, and clean mechanical energy can be derived from wind, tides, water waves, and the like. However, the energy conversion devices based on electromagnetic transducers are large in size and complex in structure, and do not meet the design and application requirements of next-generation microelectronic and nano-electronic systems. Waste energy such as human body movement, raindrops, running water and the like is ubiquitous in nature, but is almost never utilized. With advances in nanotechnology and new discoveries in energy conversion mechanisms, scientists have devised new designs of efficient and miniaturized energy conversion devices capable of collecting and converting waste energy into electrical energy through piezoelectric, triboelectric, and photovoltaic effects in an attempt to address new demands on electronic systems. The designed micro-nano generator can collect the ubiquitous clean waste energy of the nature such as human body movement, walking, vibration, wind, raindrops, running water and the like, and converts the waste energy into electric energy through the piezoelectric effect, the triboelectric effect or the photovoltaic effect and stores and utilizes the electric energy. These devices can be used not only for power generation, but also for a wide range of sensitive sensors, especially any self-powered sensor requiring power without an external power source.

The Wangzhining yard team uses the mutual coupling action of triboelectricity and electrostatic induction, and through the design of a triboelectricity pair and a device structure, a series of sensors which can collect tiny and difficultly-collected and utilized energy such as human body movement, wind power, rainwater impact and the like are prepared, and a corresponding friction Nano generator or a self-powered sensor is prepared to be applied to movement detection and human body health detection (adv. Mater.2017,29,1603115/ACS Nano 2018,12, 4280-supplement 4285/adv. Sci.2019, 1881803).

A high-performance steam-driven hydroelectric nanogenerator is prepared by performing gradient reduction on graphene oxide and regulating and controlling the interface structure of graphene and an electrode by a schoolmate team, can generate a voltage as high as 1.5V when the environmental humidity changes, and is expected to be applied to the field of self-powered miniature electronic equipment and sensors (Energy environ. Sci.2018,11, 1730-.

The Guo Vanlin teacher team prepares a hydroelectric nano-generator by using a nano-carbon material on the basis of the principle of swimming potential, can realize voltage output of up to 1.3V, and can improve output voltage or current in a series-parallel mode to light an LED lamp or supply power to a calculator (Nature nano-technology, 2017,12(4): 317).

The Penghitong teacher team takes the carbon nano tube/polymer composite fiber as a matrix and is doped with ordered mesoporous carbon to prepare the hydro-fluidic nano generator capable of generating 120mV voltage under the action of water flow. Then, after oxygen plasma treatment is carried out on the carbon nanotube fiber, the carbon nanotube fiber and another original carbon nanotube fiber form a double-electrode system, and the polarization effect of sp2 hybridized carbon atoms is utilized to prepare the hydroelectric generatorCan output power density exceeding 700mW/m in static water²Electrical energy of (Angew. chem. int. Ed.2017,56, 12940-.

The american professor ray.h. baughman reports a carbon nanotube yarn energy harvester that electrochemically converts tensile or torsional mechanical energy into electrical energy for collection and utilization, and that generates electrical energy with a power density of up to 250W/Kg during stretching, and that can be applied to collection and utilization of ocean wave energy (Science,2017,357, 773-.

All of the above studies indicate that nanomaterials are of greater interest than others due to their high specific surface area, high conductivity, and diverse macroscopic assembly forms, such as fibers, films, and three-dimensional aerogel foams. At present, although the energy conversion efficiency is lower than that of the traditional electromagnetic induction mode, the application of the micro energy conversion device based on the nano material in intelligent sensing and waste energy recycling has huge potential.

Moreover, the existing triboelectric nano-generator has a complex structure and high design requirements on triboelectric pairs, and shows sensitivity to humidity based on the mechanism of the triboelectric effect and electrostatic induction, needs strict packaging to isolate water vapor, and is not resistant to corrosion of saline-alkali environment.

Moreover, the hydropathic effect is an interaction at an interface where the surface of the nano carbon material is in contact with an environmental medium, generally needs to be in a humid environment or an aqueous solution to generate an effect, generally is a two-electrode or three-electrode system, namely needs medium assistance except a functional body, and is relatively limited in application range.

Disclosure of Invention

The invention mainly aims to provide a piezoelectric chemical fiber and a preparation method thereof, so as to overcome the defects in the prior art.

Another object of the invention is to provide the use of said piezo-chemical fibre.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a piezoelectric chemical fiber, which comprises a stretchable structure formed by conductive fibers, wherein the surface of the stretchable structure is covered with a gel electrolyte; when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between two ends, so that a voltage signal can be output.

In some preferred embodiments, the stretchable structure is formed from elastic conductive fibers.

Further, the stretchable structure includes a single-helix, double-helix, or multi-helix structure formed from conductive fibers.

The embodiment of the invention provides a preparation method of a piezoelectric chemical fiber, which comprises the following steps:

providing a conductive fiber having a large specific surface area and being drawably deformable;

and contacting a gel electrolyte with the surface of the conductive fiber to obtain the piezoelectric chemical fiber, wherein when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between the two ends of the piezoelectric chemical fiber, so that a voltage signal can be output.

The embodiment of the invention also provides the piezoelectric chemical fiber prepared by the method.

The embodiment of the invention also provides application of the piezoelectric chemical fiber in preparation of a flexible nano generator or a self-powered sensor.

The embodiment of the invention also provides an energy conversion mechanism which comprises the piezoelectric chemical fiber.

The embodiment of the invention also provides an energy conversion method, which comprises the following steps:

providing the aforementioned piezo-chemical fiber; and

and applying mechanical stimulation to the piezoelectric chemical fiber to generate a potential difference at two ends of the piezoelectric chemical fiber and output a voltage signal to realize conversion from mechanical energy to electric energy.

Compared with the prior art, the invention has the beneficial effects that:

1) the invention creatively discovers a new interaction phenomenon at the contact interface of the material surface and the electrolyte, and can be applied to a flexible nano generator or a self-powered sensor with simple structure, no need of assistance of other additional devices and wide application range;

2) the piezoelectric chemical fiber structure and the preparation process are simple, can be realized by directly coating a layer of gel electrolyte on the surface of the conductive fiber with large specific surface area, is a single electrode system, and does not need to additionally realize the output of voltage difference by means of a counter electrode or a reference electrode;

3) the piezoelectric chemical fiber can be applied in various environments after being simply packaged, and can work well in air or liquid no matter in a wet or dry environment.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a flow chart of the preparation of a novel piezochemical fiber according to an exemplary embodiment of the present invention.

FIGS. 2a and 2b are respectively a PVA/H coated with a piezoelectric chemical fiber prepared in example 1 of the present invention₂SO₄And (3) a measured voltage data graph of the gel electrolyte under different frequencies and different strains.

FIG. 2c shows the pure fibers, fibers + PVA, and fibers + PVA/H in example 1 of the present invention₂SO₄Comparative schematic of gel electrolyte.

Fig. 2d and fig. 2e are graphs of measured voltage data at different frequencies and different strains after the piezoelectric chemical fiber prepared in example 2 of the present invention is coated with PVA/KOH gel electrolyte.

FIG. 2f shows the pure fibers, fiber + PVA, and fiber + PVA/H in example 2 of the present invention₂SO₄Comparative schematic of gel electrolyte.

FIG. 3 shows the preparation of a piezoelectric chemical fiber in different gel electrolytes PVA/KOH and PVA/H according to an exemplary embodiment of the present invention₂SO₄Schematic diagram of the output signal in (1).

FIG. 4 shows an embodiment of the present inventionPiezo-chemical fiber coated PVA/H prepared in example 2₂SO₄A plot of measured voltage data for tests performed at different tensile frequencies after gelling the electrolyte.

FIG. 5 is a view showing that the piezoelectric chemical fiber-coated PVA/H prepared in example 3 of the present invention₂SO₄A plot of measured voltage data for tests performed at different tensile frequencies after gelling the electrolyte.

FIG. 6 is a view of the PVA/H coated with piezoelectric chemical fiber prepared in example 4 of the present invention₂SO₄A plot of measured voltage data for tests performed at different tensile frequencies after gelling the electrolyte.

Detailed Description

In view of the defects in the prior art, the inventor of the present invention has made long-term research and extensive practice to provide a technical scheme of the present invention, and intends to research a new energy conversion mode based on the contact interaction between the material surface and the environmental medium, i.e., a single electrode structure mode in which the surface of the conductive fiber with a large specific surface area is coated with the gel electrolyte, so as to realize the preparation of a flexible nano-generator or self-powered sensor with a simple structure, without the assistance of other additional devices, and a wide application range.

Referring to fig. 1, the principle of the novel piezoelectric chemical fiber provided by the present invention is based on the interaction between the material surface and the contact interface of the electrolyte, and when the fiber is at rest, an electrochemical double layer is formed at the interface, and the charges are uniformly distributed along the length direction of the fiber; when the fiber is stretched asymmetrically, the stretching deformation of the spiral structure cannot follow the force transmission, the deformation is relaxed, the specific surface area in the fiber direction is unevenly changed, the charge density gradient is unevenly distributed, the potential difference at two ends of the fiber is different, and voltage signal output is generated. Based on the principle, the special piezoelectric chemical process requires that the fiber material has larger specific surface area, certain mechanical strength and good flexibility and elasticity while conducting.

An aspect of an embodiment of the present invention provides a piezoelectric chemical fiber, which includes a stretchable structure formed of a conductive fiber, and a surface of the stretchable structure is covered with a gel electrolyte; when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between two ends, so that a voltage signal can be output.

In some embodiments, the stretchable structure is formed from elastic conductive fibers.

In some embodiments, the stretchable structure includes a single helix, a double helix, or a multiple helix structure formed from conductive fibers, and the like, but is not limited thereto.

Further, the stretchable structure includes a spiral structure formed by twisting the conductive fiber in a stretched state.

Further, the stretchable structure includes a double spiral structure formed by self-twisting conductive fibers having a single spiral structure formed by twisting the conductive fibers in a stretched state.

In some embodiments, the stretchable structure comprises a spring structure formed from conductive fibers.

In some embodiments, the mechanical stimulus includes any one or combination of asymmetric stretching, twisting, bending, and the like, but is not limited thereto.

Further, the specific surface area of the piezoelectric chemical fiber is more than 100m²The mechanical strength is more than 150 MPa.

Further, the conductive fiber includes any one or a combination of two or more of carbon nanotube fiber, graphene fiber, conductive polymer fiber, carbon material/polymer composite fiber, and the like, but is not limited thereto.

One aspect of the embodiments of the present invention provides a method for preparing a piezoelectric chemical fiber, including:

providing a conductive fiber having a large specific surface area and being drawably deformable;

and contacting a gel electrolyte with the surface of the conductive fiber to obtain the piezoelectric chemical fiber, wherein when mechanical stimulation is applied to the piezoelectric chemical fiber, a potential difference is generated between the two ends of the piezoelectric chemical fiber, so that a voltage signal can be output.

Further, the specific surface area of the conductive fiber is more than 100m²A/g, preferably greater than 120m²The larger the value of the ratio/gGood), the tensile strength is more than 150MPa, the larger the better.

In some embodiments, the conductive fibers can form a stretchable structure, preferably a stretchable structure such as a tight helical structure or a loose spring structure, but not limited thereto.

For example, the stretchable structure includes a single helix, a double helix, or a multiple helix structure formed of conductive fibers, etc., but is not limited thereto.

In some embodiments, the conductive fibers comprise elastic conductive fibers or inelastic conductive fibers, wherein for elastic conductive fibers, straight fibers are possible, while inelastic conductive fibers must increase the stretchability of the fibers by means of a stretchable structure such as a helical structure. In addition, the fibers used in the present invention must have a certain conductivity.

Further, if the conductive fiber itself has a good elasticity, the twisting step can be omitted, but it is preferable to secure the structure of the coil spring, so that the structural asymmetry generated during the stretching can be sufficiently exerted, and the deformation range can be greatly improved.

Further, the conductive fiber includes any one or a combination of two or more of carbon nanotube fiber, graphene fiber, conductive polymer fiber, carbon material/polymer composite fiber, and the like, but is not limited thereto.

In some embodiments, the method of making comprises: and twisting the conductive fiber in a stretching state to obtain the spiral conductive fiber.

Furthermore, the speed of twisting treatment is 60-300 r/min. The twisting speed of the invention can be within 60-300r/min, the too slow twisting speed leads to overlong twisting time, and the too fast twisting speed easily leads to uneven spiral structure after twisting, so the best twisting speed is between 60-300 r/min.

Furthermore, the twist of the spiral conductive fiber is 15000 to 30000 r/m.

In some embodiments, the method of making further comprises: and self-stranding the spiral conductive fiber to form the double-spiral conductive fiber. Compared with a single-spiral structure, the double-spiral structure has the advantages of better self-supporting property and better circulation stability, so that the double-spiral structure can be used as a more preferable scheme.

In some embodiments, the stretchable structure comprises a spring structure formed from conductive fibers.

In some embodiments, the method of making comprises: coating and wrapping the surface of the stretchable structure with gel electrolyte to obtain the piezoelectric chemical fiber.

Further, the gel electrolyte includes a PVA (polyvinyl alcohol) -based gel electrolyte, wherein the electrolyte includes an acid (e.g., H)₂SO₄) A base (e.g., KOH), a chloride salt, or the like, and may be other conductive hydrogels, but is not limited thereto.

In some embodiments, the mechanical stimulus includes any one or combination of asymmetric stretching, twisting, bending, and the like, but is not limited thereto.

In some more preferred embodiments, according to the flow chart of fig. 1, a novel piezo-chemical fiber is prepared as follows:

1. selecting conductive fibers (carbon nanotube fibers, graphene fibers, conductive polymer fibers and conductive composite fibers) with a certain length, tying one end of the conductive fibers to a rotating motor, hanging a weight at the other end of the conductive fibers to apply a certain stress, twisting at a speed of 200r/min (no special requirement on the rotating speed) until a spiral structure (a) is completely formed, preparing spiral conductive fibers (b), wherein the twist is about 24000r/m, and the elasticity and tensile strain of the conductive fibers can be greatly improved in the form of the spiral structure. In order to facilitate the test, two silver wires are respectively connected with two ends of the conductive fiber to be used as electrodes and connected with a universal meter or a data acquisition card, the joint of the silver wires and the conductive fiber is insulated by epoxy resin in a heat sealing way so as to avoid the contact corrosion between the silver wires and the conductive fiber in the electrolyte to influence the accuracy of the experiment, and then the prepared gel electrolyte is coated and wrapped on the conductive spiral fiber (c). When in test, one end of the spiral conductive fiber is fixed, and the other end is circularly stretched, so that voltage signals can be generated at the two ends of the spiral conductive fiber, and the signals can be collected and recorded by a digital multimeter or a data acquisition card. In addition, in order to improve the tensile stability and the cycle life of the spiral conductive fiber, the inventor designs the self-plied double-spiral conductive fiber, and the preparation process comprises the following steps: the single-spiral conductive fiber (b) is horizontally placed and fixed at two ends, a weight (d) is hung in the middle of the single-spiral conductive fiber, then the two ends of the single-spiral conductive fiber are closed, the single-spiral conductive fiber is self-stranded under the action of gravity of the weight and self large torque to form stable double-spiral conductive fiber (e), silver wires are connected at the two ends of the double-spiral conductive fiber in a similar manner, epoxy resin is used for insulation, and gel electrolyte is coated to complete the preparation (f) of the double-spiral piezoelectric chemical fiber.

Another aspect of the embodiments of the present invention provides a piezoelectric chemical fiber prepared by the foregoing method, wherein the piezoelectric chemical fiber generates a potential difference between two ends when a mechanical stimulus is applied, so as to output a voltage signal.

Further, the mechanical stimulus includes any one or a combination of more of asymmetric stretching, twisting, bending, and the like, but is not limited thereto.

Another aspect of the embodiments of the present invention also provides an application of the piezoelectric chemical fiber in the preparation of a flexible nano-generator or a self-powered sensor.

The piezoelectric chemical fiber can be applied in various environments after being simply packaged, and can work well in air or liquid no matter in a wet or dry environment.

Another aspect of an embodiment of the present invention also provides an energy conversion mechanism, which includes the aforementioned piezoelectric chemical fiber.

Furthermore, two ends of the piezoelectric chemical fiber are respectively connected with electrodes.

Furthermore, two ends of the stretchable structure are respectively connected with an electrode in an insulating and sealing manner.

Another aspect of an embodiment of the present invention also provides an energy conversion method, including:

providing the aforementioned piezo-chemical fiber; and

and applying mechanical stimulation to the piezoelectric chemical fiber to generate a potential difference at two ends of the piezoelectric chemical fiber and output a voltage signal to realize conversion from mechanical energy to electric energy.

In conclusion, the piezoelectric chemical fiber structure and the preparation process are simple, the piezoelectric chemical fiber structure can be realized by directly coating a layer of gel electrolyte on the surface of the conductive fiber with the large specific surface area, and the piezoelectric chemical fiber structure is a single electrode system, and the voltage difference output is realized without additionally using a counter electrode or a reference electrode.

The present invention is further illustrated by the following examples and figures, but it should not be construed that the scope of the subject matter set forth herein is limited to the examples set forth below. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.

Example 1

The preparation process of the novel piezoelectric chemical fiber in the embodiment is specifically as follows:

referring to fig. 1, a carbon nanotube fiber with a certain length is selected, one end of the carbon nanotube fiber is tied to a rotating motor, a weight is hung at one end of the carbon nanotube fiber to apply a certain stress, the carbon nanotube fiber is twisted at a speed of 200r/min until a spiral structure (a) is completely formed, a spiral conductive fiber (b) is prepared, the twist is about 24000r/m, and the elasticity and tensile strain of the conductive fiber can be greatly improved by the spiral structure. In order to facilitate the test, two silver wires are respectively connected with two ends of the conductive fiber to be used as electrodes and connected with a universal meter or a data acquisition card, the joint of the silver wires and the conductive fiber is insulated by epoxy resin in a heat sealing way so as to avoid the contact corrosion between the silver wires and the conductive fiber in the electrolyte to influence the accuracy of the experiment, and then the prepared gel electrolyte is coated and wrapped on the conductive spiral fiber (c). When in test, one end of the spiral conductive fiber is fixed, and the other end is circularly stretched, so that voltage signals can be generated at the two ends of the spiral conductive fiber, and the signals can be collected and recorded by a digital multimeter or a data acquisition card. In addition, in order to improve the tensile stability and the cycle life of the spiral conductive fiber, the inventor designs the self-plied double-spiral conductive fiber, and the preparation process comprises the following steps: the single-spiral conductive fiber (b) is horizontally placed and fixed at two ends, a weight (d) is hung in the middle of the single-spiral conductive fiber, then the two ends of the single-spiral conductive fiber are closed, the single-spiral conductive fiber is self-stranded under the action of gravity of the weight and self large torque to form stable double-spiral conductive fiber (e), silver wires are connected at the two ends of the double-spiral conductive fiber in a similar manner, epoxy resin is used for insulation, and gel electrolyte is coated to complete the preparation (f) of the double-spiral piezoelectric chemical fiber.

The inventor also coats PVA/H respectively on the piezoelectric chemical fiber prepared by the steps₂SO₄And PVA/KOH gel electrolyte, measuring voltage data diagram at different frequencies and different strains, and performing pure fiber, fiber + PVA (without H)₂SO₄Or electrolyte such as KOH) and fiber + PVA/H₂SO₄Or a contrast test of KOH electrolyte liquid, the unique capacity phenomenon of the novel piezoelectric fiber under deformation is verified.

Referring to FIGS. 2a and 2b, the PVA/H coated with piezoelectric chemical fiber prepared in this example is shown₂SO₄And (3) a measured voltage data graph of the gel electrolyte under different frequencies and different strains. FIG. 2c shows the pure fibers, fiber + PVA, and fiber + PVA/H in this example₂SO₄Comparative schematic of gel electrolyte.

Fig. 2d and 2e show graphs of measured voltage data at different frequencies and different strains after the piezoelectric chemical fiber prepared in this example is coated with PVA/KOH gel electrolyte. FIG. 2f shows the pure fibers, fiber + PVA, and fiber + PVA/H in this example₂SO₄Comparative schematic of gel electrolyte.

FIG. 3 shows the piezoelectric chemical fibers in different gel electrolytes of PVA/KOH and PVA/H₂SO₄The output signals of the piezoelectric chemical fibers in different gel electrolytes have different polarities (positive and negative in PVA/KOH, PVA/H)₂SO₄Negative first then positive).

Example 2

Graphene Oxide (GO) fibers prepared by solution spinning are reduced to obtain graphene fibers (rGO), referring to fig. 1, one end of each graphene fiber with a certain length is tied to a rotating motor, a weight is hung at one end of each graphene fiber to apply certain stress, the graphene fibers are twisted at the speed of 300r/min until a spiral structure (a) is completely formed, spiral conductive fibers (b) are prepared, and the twist degree is about 30000 r/m. Connecting two silver wires with two ends of the conductive fiber respectively to be used as electrodes, connecting the electrodes with a universal meter or a data acquisition card, thermally sealing and insulating the joint of the silver wires and the conductive fiber by using epoxy resin to avoid the contact corrosion between the silver wires and the conductive fiber in electrolyte to influence the accuracy of the experiment, and coating the prepared gel electrolyte on the conductive spiral fiber (c). When in test, one end of the spiral conductive fiber is fixed, and the other end is circularly stretched, so that voltage signals can be generated at the two ends of the spiral conductive fiber, and the signals can be collected and recorded by a digital multimeter or a data acquisition card.

The inventor coats PVA/H on the piezoelectric chemical fiber prepared by the steps₂SO₄The gel electrolyte was then tested at different tensile frequencies and the voltage data plot found is shown in figure 4.

Example 3

The PVA/PEDOT: PSS/DMSO conductive polymer fiber prepared by electrostatic spinning is used as a raw material, referring to fig. 1, one end of the polymer fiber with a certain length is tied to a rotating motor, a weight is hung at one end of the polymer fiber to apply a certain stress, the polymer fiber is twisted at the speed of 60r/min until a spiral structure (a) is completely formed, and a spiral conductive fiber (b) is prepared, wherein the twist degree is about 18000 r/m. Connecting two silver wires with two ends of the conductive fiber respectively to be used as electrodes, connecting the electrodes with a universal meter or a data acquisition card, thermally sealing and insulating the joint of the silver wires and the conductive fiber by using epoxy resin to avoid the contact corrosion between the silver wires and the conductive fiber in electrolyte to influence the accuracy of the experiment, and coating the prepared gel electrolyte on the conductive spiral fiber (c). When in test, one end of the spiral conductive fiber is fixed, and the other end is circularly stretched, so that voltage signals can be generated at the two ends of the spiral conductive fiber, and the signals can be collected and recorded by a digital multimeter or a data acquisition card.

The inventor coats PVA/H on the piezoelectric chemical fiber prepared by the steps₂SO₄The gel electrolyte was then tested at different tensile frequencies and the voltage data plot found is shown in figure 5.

Example 4

PSS composite fiber prepared by solution spinning is taken as a raw material, referring to fig. 1, one end of polymer fiber with a certain length is tied to a rotating motor, a weight is hung at one end of the polymer fiber to apply a certain stress, the polymer fiber is twisted at the speed of 300r/min until a spiral structure (a) is completely formed, and spiral conductive fiber (b) is prepared, wherein the twist degree is about 15000 r/m. Connecting two silver wires with two ends of the fiber respectively to serve as electrodes, connecting the two silver wires with a universal meter or a data acquisition card, thermally sealing and insulating the joint of the silver wires and the conductive fiber by using epoxy resin to avoid contact corrosion between the silver wires and the conductive fiber in electrolyte to influence the accuracy of the experiment, and coating the prepared gel electrolyte on the conductive spiral fiber (c). When in test, one end of the spiral conductive fiber is fixed, and the other end is circularly stretched, so that voltage signals can be generated at the two ends of the spiral conductive fiber, and the signals can be collected and recorded by a digital multimeter or a data acquisition card.

The inventor coats PVA/H on the piezoelectric chemical fiber prepared by the steps₂SO₄The gel electrolyte was then tested at different tensile frequencies and the voltage data plot found is shown in figure 6.

By means of the embodiment, the novel interaction phenomenon at the contact interface of the material surface and the electrolyte is discovered in an original way, the preparation process is simple, the method can be realized by directly coating a layer of gel electrolyte on the surface of the conductive fiber with large specific surface area, and the single-electrode system is adopted, and the output of voltage difference is realized without additionally using a counter electrode or a reference electrode; moreover, the piezoelectric chemical fiber can be applied to various environments after being simply packaged, and can be applied to the fields of preparing flexible nano generators or self-powered sensors with simple structures, no need of assistance of other additional devices and wide application range.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.