阅读说明：本技术 可穿戴摩擦电纳米发电机、设备及其制备方法 (Wearable triboelectric nano generator, wearable triboelectric nano generator equipment and preparation method of wearable triboelectric nano generator ) 是由 龙云泽 宋威志 邱荟静 王晓雄 王宁 吴俊鹏 于 2020-12-02 设计创作，主要内容包括：本申请实施例公开了一种可穿戴摩擦电纳米发电机、设备及其制备方法,所示可穿戴摩擦电纳米发电机,包括：第一摩擦层和第二摩擦层,所述第一摩擦层依次包括电极层、粘连层、介电层和摩擦负极材料层,所述第二摩擦层依次包括摩擦正极材料层、介电层、粘连层和电极层,所述电极层为导电织物,所述导电织物包括非金属织物,所述非金属织物上聚合聚苯胺,所述第一摩擦层和第二摩擦层的位置关系被配置为：所述摩擦负极材料层和所述摩擦正极材料层相对设置。在本申请实施例中,以传统织物作为可穿戴摩擦电纳米发电机的电极层,使得可穿戴摩擦电纳米发电机具有很高的柔性,可以和普通织物一样折叠、拉伸或弯曲。(The embodiment of the application discloses a wearable triboelectric nano-generator, a device and a preparation method thereof, wherein the wearable triboelectric nano-generator comprises: first frictional layer and second frictional layer, first frictional layer includes electrode layer, adhesion layer, dielectric layer and friction negative material layer in proper order, the second frictional layer includes friction positive material layer, dielectric layer, adhesion layer and electrode layer in proper order, the electrode layer is conductive fabric, conductive fabric includes non-metal fabric, the last polyaniline that polymerizes of non-metal fabric, the position relation of first frictional layer and second frictional layer is configured into: the friction negative electrode material layer and the friction positive electrode material layer are oppositely arranged. In the embodiment of the application, the traditional fabric is used as an electrode layer of the wearable triboelectric nano-generator, so that the wearable triboelectric nano-generator has high flexibility and can be folded, stretched or bent like a common fabric.)

1. A wearable triboelectric nanogenerator, comprising: first frictional layer and second frictional layer, first frictional layer includes electrode layer, adhesion layer, dielectric layer and friction negative material layer in proper order, the second frictional layer includes friction positive material layer, dielectric layer, adhesion layer and electrode layer in proper order, the electrode layer is conductive fabric, conductive fabric includes non-metal fabric, the last polyaniline that polymerizes of non-metal fabric, the position relation of first frictional layer and second frictional layer is configured into: the friction negative electrode material layer and the friction positive electrode material layer are oppositely arranged, the first friction layer and the second friction layer can relatively move, and when the first friction layer and the second friction layer can relatively move, a potential difference is generated between the first friction layer and the second friction layer.

2. The wearable triboelectric nanogenerator of claim 1, wherein the adhesion layer is polycaprolactone, the dielectric layer is polyurethane, the friction negative material layer is polytetrafluoroethylene or a polytetrafluoroethylene derivative, and the friction positive material layer is nylon.

3. The wearable triboelectric nanogenerator of claim 2, wherein the non-metallic fabric is nylon, cotton, acrylic, polyester and/or fiber.

4. The wearable triboelectric nanogenerator according to claim 1, wherein the thickness of the electrode layer is 500-600 μm.

5. The wearable triboelectric nanogenerator according to claim 1, wherein the thickness of the adhesion layer is 10-20 μ ι η.

6. The wearable triboelectric nanogenerator according to claim 1, wherein the thickness of the dielectric layer is 20-30 μ ι η.

7. Wearable triboelectric nanogenerator according to claim 1, wherein the triboelectric negative material layer and/or triboelectric positive material layer has a thickness of 20-30 μ ι η.

8. A preparation method of a wearable triboelectric nano-generator is characterized by comprising the following steps:

carrying out in-situ polymerization on polyaniline on a non-metal fabric to obtain an electrode layer, wherein the substrate of the electrode layer is the non-metal fabric;

sequentially and electrostatically spinning polycaprolactone, polyurethane and polytetrafluoroethylene or polytetrafluoroethylene derivatives on the electrode layer, and/or sequentially and electrostatically spinning polycaprolactone, polyurethane and nylon on the electrode layer;

and carrying out hot-pressing treatment on the material obtained by electrostatic spinning to obtain a first friction layer and/or a second friction layer, wherein the first friction layer sequentially comprises an electrode layer, a polycaprolactone layer, a polyurethane layer and polytetrafluoroethylene or polytetrafluoroethylene derivative layer, and the second friction layer sequentially comprises an electrode layer, a polycaprolactone layer, a polyurethane layer and a nylon layer.

9. A respiratory monitoring device comprising a first friction layer and a second friction layer according to any one of claims 1 to 7;

the positional relationship of the first friction layer and the second friction layer is configured to: when the user uses when breathing monitoring facilities, first frictional layer with the overlapping of second frictional layer sets up and constitutes the friction electricity nanometer generator, and when user's respiratory state is different, state of relative motion of first frictional layer with the second frictional layer is different, the different electric signal of friction electricity nanometer generator output.

10. An information transmission apparatus, characterized by a glove and a touch electrode;

the glove is made using the first friction layer of any one of claims 1-7, and the touch electrode is made using the second friction layer of any one of claims 1-7; alternatively, the glove is made with the second friction layer of any of claims 1-7, and the touch electrode is made with the first friction layer of any of claims 1-7;

when the glove is used by a user, the user wears the glove and touches the touch electrode through the glove to output a corresponding electric signal.

Technical Field

The application relates to the technical field of triboelectric nanogenerators, in particular to a wearable triboelectric nanogenerator, wearable triboelectric nanogenerator equipment and a preparation method of the wearable triboelectric nanogenerator.

Background

A Triboelectric nanogenerator (TENG) is an energy generating unit, in an internal circuit of which, due to a Triboelectric effect, charge transfer occurs between two thin layers of friction materials with different Triboelectric polarities, so that a potential difference is formed between the two thin layers; in the external circuit, electrons flow between two electrodes respectively stuck on the back surface of the friction material layer or between the electrodes and the ground under the driving of the potential difference, so that the potential difference is balanced. The device has the characteristics of small volume and capability of converting weak mechanical energy into electric energy for output.

In the wearable application field, the metal electrode of the triboelectric nano generator has certain hardness, so that the metal electrode has great influence on the flexibility of a wearable device. For example, in the related art, in which a metal copper foil is included in a metal electrode of a triboelectric nanogenerator, stress distribution on the metal copper foil is more concentrated than that of a stretchable polymer friction layer, and the metal material is generally unstable under sweat erosion, resulting in poor sweat corrosion resistance. These problems severely limit the application of triboelectric nanogenerators in wearable applications.

Disclosure of Invention

The embodiment of the application provides a wearable triboelectric nano-generator, wearable triboelectric nano-generator equipment and a preparation method of wearable triboelectric nano-generator, and aims to solve the problem that the wearable triboelectric nano-generator in the prior art is poor in flexibility.

In a first aspect, an embodiment of the present application provides a wearable triboelectric nanogenerator, including: first frictional layer and second frictional layer, first frictional layer includes electrode layer, adhesion layer, dielectric layer and friction negative material layer in proper order, the second frictional layer includes friction positive material layer, dielectric layer, adhesion layer and electrode layer in proper order, the electrode layer is conductive fabric, conductive fabric includes non-metal fabric, the last polyaniline that polymerizes of non-metal fabric, the position relation of first frictional layer and second frictional layer is configured into: the friction negative electrode material layer and the friction positive electrode material layer are oppositely arranged, the first friction layer and the second friction layer can relatively move, and when the first friction layer and the second friction layer can relatively move, a potential difference is generated between the first friction layer and the second friction layer.

Preferably, the adhesion layer is polycaprolactone, the dielectric layer is polyurethane, the friction negative material layer is polytetrafluoroethylene or a polytetrafluoroethylene derivative, and the friction positive material layer is nylon.

Preferably, the non-metal fabric is nylon, cotton, acrylic, polyester and/or fiber.

Preferably, the thickness of the electrode layer is 500-.

Preferably, the thickness of the adhesion layer is 10 to 20 μm.

Preferably, the thickness of the dielectric layer is 20-30 μm.

Preferably, the thickness of the friction negative electrode material layer and/or the friction positive electrode material layer is 20-30 μm.

In a second aspect, an embodiment of the present application provides a method for preparing a wearable triboelectric nanogenerator, including:

carrying out in-situ polymerization on polyaniline on a non-metal fabric to obtain an electrode layer, wherein the substrate of the electrode layer is the non-metal fabric;

sequentially and electrostatically spinning polycaprolactone, polyurethane and polytetrafluoroethylene or polytetrafluoroethylene derivatives on the electrode layer, and/or sequentially and electrostatically spinning polycaprolactone, polyurethane and nylon on the electrode layer;

and carrying out hot-pressing treatment on the material obtained by electrostatic spinning to obtain a first friction layer and/or a second friction layer, wherein the first friction layer sequentially comprises an electrode layer, a polycaprolactone layer, a polyurethane layer and polytetrafluoroethylene or polytetrafluoroethylene derivative layer, and the second friction layer sequentially comprises an electrode layer, a polycaprolactone layer, a polyurethane layer and a nylon layer.

In a third aspect, embodiments of the present application provide a respiration monitoring apparatus comprising a first friction layer and a second friction layer according to any one of the first aspect;

the positional relationship of the first friction layer and the second friction layer is configured to: when the user uses when breathing monitoring facilities, first frictional layer with the overlapping of second frictional layer sets up and constitutes the friction electricity nanometer generator, and when user's respiratory state is different, state of relative motion of first frictional layer with the second frictional layer is different, the different electric signal of friction electricity nanometer generator output.

In a fourth aspect, embodiments of the present application provide an information transmission device, a glove and a touch electrode;

the glove is made using the first friction layer of any of the first aspects, and the touch electrode is made using the second friction layer of any of the first aspects; alternatively, the glove is made with the second friction layer of any of the first aspects, and the touch electrode is made with the first friction layer of any of the first aspects;

when the glove is used by a user, the user wears the glove and touches the touch electrode through the glove to output a corresponding electric signal.

In the embodiment of the application, the traditional fabric is used as an electrode layer of the wearable triboelectric nano-generator, so that the wearable triboelectric nano-generator has high flexibility and can be folded, stretched or bent like a common fabric.

Drawings

In order to more clearly illustrate the embodiments of the present application 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, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

Fig. 1 is a schematic structural diagram of a wearable triboelectric nano-generator according to an embodiment of the present disclosure;

fig. 2 is a scanning electron microscope image according to an embodiment of the present disclosure;

fig. 3 is a schematic flow chart of a method for manufacturing a wearable triboelectric nanogenerator according to an embodiment of the present application;

FIG. 4 is a schematic diagram of an output signal of a respiration monitoring device according to an embodiment of the present disclosure;

fig. 5 is a schematic diagram of an output signal of an information transmission apparatus according to an embodiment of the present application;

FIG. 6 is a schematic diagram of an output voltage signal before and after a resistive sensor introduces a contact resistance;

fig. 7 is a schematic diagram of an output voltage signal before and after a wearable triboelectric nanogenerator introduces a contact resistance according to an embodiment of the application.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Fig. 1 is a schematic structural diagram of a wearable triboelectric nanogenerator provided by an embodiment of the present application, and fig. 2 is an electron microscope scanning image provided by the embodiment of the present application, wherein fig. 2(a) is a non-metal fabric, fig. 2(b) is a non-metal fabric after polyaniline polymerization, fig. 2(c) is a polycaprolactone nanofiber membrane, fig. 2(d) is a polyurethane nanofiber membrane, fig. 2(e) is a polytetrafluoroethylene nanofiber membrane, and fig. 2(f) is a nylon nanofiber membrane. As shown in fig. 1 in combination with fig. 2, the wearable triboelectric nanogenerator comprises: the first friction layer 110 sequentially comprises an electrode layer 101, an adhesion layer 102, a dielectric layer 103 and a friction negative material layer 104, the first friction layer 110 sequentially comprises a friction positive material layer 105, a dielectric layer 103, an adhesion layer 102 and an electrode layer 101, the electrode layer 101 is a conductive fabric, the conductive fabric comprises a non-metal fabric, polyaniline is polymerized on the non-metal fabric, and the non-metal fabric forms a fabric substrate with a conductive property and has conductivity by polymerizing the polyaniline on the non-metal fabric.

The positional relationship of the first friction layer 110 and the second friction layer 120 is configured to: the friction anode material layer 104 and the friction cathode material layer 105 are oppositely arranged, the first friction layer 110 and the second friction layer 120 can relatively move, and when the first friction layer 110 and the second friction layer 120 can relatively move, a potential difference is generated between the first friction layer 110 and the second friction layer 120.

In an alternative embodiment, the non-metal fabric is nylon, cotton, acrylic, polyester and/or fiber, and the thickness of the electrode layer 101 is 500-600 μm.

In an alternative embodiment, the adhesion layer 102 is a polycaprolactone nanofiber film, specifically, a low melting point polycaprolactone, which serves as a bonding agent between the electrode layer 101 and the dielectric layer 103, and may have a thickness of 10-20 μm.

In an alternative embodiment, the dielectric layer 103 is a polyurethane nanofiber film, in particular, thermoplastic polyurethane, the average fiber diameter of the polyurethane nanofiber film is about 400nm, and the thickness of the dielectric layer 103 is 20-30 μm.

In an alternative embodiment, the friction negative material layer 104 is a polytetrafluoroethylene or polytetrafluoroethylene derivative nanofiber membrane, the average fiber diameter of the polytetrafluoroethylene or polytetrafluoroethylene derivative fiber membrane is about 970nm, and the thickness of the friction negative material layer 104 is 20-30 μm.

In an alternative embodiment, the triboelectric positive electrode material layer 105 is a nylon nanofiber membrane with fibers having an average diameter of about 120nm, and the triboelectric positive electrode material layer 105 has a thickness of 20-30 μm.

In the embodiment of the application, the traditional fabric is used as an electrode layer of the wearable triboelectric nano-generator, so that the wearable triboelectric nano-generator has high flexibility and can be folded, stretched or bent like a common fabric.

Fig. 3 is a schematic flow chart of a method for manufacturing a wearable triboelectric nanogenerator according to an embodiment of the present application, as shown in fig. 3, the method mainly includes the following steps.

Step S301: carrying out in-situ polymerization on polyaniline on a non-metal fabric to obtain an electrode layer, wherein the substrate of the electrode layer is the non-metal fabric.

Step S302: and (2) electrostatic spinning polycaprolactone, polyurethane and polytetrafluoroethylene or polytetrafluoroethylene derivatives on the electrode layer in sequence, and/or electrostatic spinning polycaprolactone, polyurethane and nylon on the electrode layer in sequence.

Step S303: and carrying out hot-pressing treatment on the material obtained by electrostatic spinning to obtain a first friction layer and/or a second friction layer.

Wherein, first frictional layer includes electrode layer, polycaprolactone layer, polyurethane layer and polytetrafluoroethylene or polytetrafluoroethylene derivative layer in proper order, second frictional layer includes electrode layer, polycaprolactone layer, polyurethane layer and nylon layer in proper order.

Specifically, the preparation environment temperature of the polycaprolactone layer is 27 +/-3 ℃, and the atmospheric humidity is 55 +/-5%. In the case of electrospinning, the polymer (polycaprolactone) solution was discharged at a constant flow rate of 0.5mL/h, the voltage applied to the syringe needle (injector for polymer solution) was 12kV, and the spinning distance was 15cm, i.e., the injector for polymer solution was 15cm from the receiving plate.

The preparation environment temperature of the polyurethane layer is 25 +/-3 ℃, the atmospheric humidity is 42 +/-5%, the polymer (polyurethane) solution is discharged at a constant flow rate of 1mL/h, the applied voltage of a syringe needle (an ejector of the polymer solution) is 13kV, and the spinning distance is 15 cm.

The preparation environment temperature of the polytetrafluoroethylene or polytetrafluoroethylene derivative layer is 25 +/-3 ℃, the atmospheric humidity is 42 +/-5%, the polymer (polytetrafluoroethylene or polytetrafluoroethylene derivative) solution is discharged at a constant flow rate of 1mL/h, the voltage applied to a syringe needle (an ejector of the polymer solution) is 15kV, and the spinning distance is 15 cm.

The preparation environment temperature of the nylon layer is 24 +/-3 ℃, the atmospheric humidity is 47 +/-5%, the polymer (nylon) solution is discharged at a constant flow rate of 0.5mL/h, the voltage applied by a syringe needle (an ejector of the polymer solution) is 16kV, and the spinning distance is 15 cm.

Because the electrode layers in the first friction layer and the second friction layer prepared by the method are prepared based on the traditional fabric, the wearable triboelectric nano-generator assembled by the electrode layers has high flexibility and can be folded, stretched or bent like the common fabric.

The wearable triboelectric nano generator provided by the embodiment of the application can be applied to various wearable fields. For example, the wearable triboelectric nano-generator can be used for preparing a respiration monitoring device for medical detection. The details will be described below.

Traditional respiration monitoring is usually based on a mask type sensor, but the mode requires a patient to wear the mask for a long time, and is easy to cause the breathing disorder of the patient. The breathing monitoring equipment that embodiment of this application was prepared based on wearable triboelectric nanogenerator principle includes first frictional layer and second frictional layer, when this breathing monitoring equipment was worn to the patient, first frictional layer with the second frictional layer overlaps to set up and constitutes the triboelectric nanogenerator. For example, the first friction layer and the second friction layer are respectively arranged at two ends of the elastic bandage, and the patient wraps the elastic bandage around the chest of the patient, wherein the first friction layer and the second friction layer are overlapped in front of the chest of the patient to form the triboelectric nano-generator. It can be understood that, along with the change of the breathing rhythm of the patient, the contour volume of the chest cavity of the patient changes, so that the first friction layer and the second friction layer at the two ends of the bandage are caused to move relatively, and an electric signal is output. When the breathing rhythm of the patient is different, the output electric signals are different.

Fig. 4 is a schematic diagram of an output signal of a respiration monitoring device according to an embodiment of the present disclosure, as shown in fig. 4, when a patient wears the respiration monitoring device, Normal breathing (Normal breathing), Deep breathing (Deep breathing), and Rapid breathing (Rapid breathing) are output according to different signals, so that a respiratory state of the patient can be determined based on the output signal.

In addition, in order to avoid serious consequences caused by long-term respiration stopping, a Warning Threshold (Warning Threshold) mode can be set to assist in alarming. When the output signal is lower than a set alarm threshold value and the duration time exceeds 10s, an alarm signal is sent out, for example, an indicator lamp is flickered or an alarm is sent out through a loudspeaker, and the like, so that medical personnel are reminded of emergency rescue.

The respiration monitoring device is also suitable for nursing critically ill patients or preventing the drowning of children. Of course, the device can also be worn on the body of the athlete to evaluate the physiological signals and the physical and kinematic performance indexes of the athlete in the process of sports. During training, the breathing frequency of the athlete can be timely detected and collected through an analog-digital conversion circuit and a buffer. The movement of the wearer is more natural without connecting any external equipment, and certain portability and comfort are realized.

The wearable triboelectric nano-generator provided by the embodiment of the application can be applied to real-time communication. For example, for a particular patient wearing a respiratory mask or unable to speak, remote communication using fingers is an important option, such as Hodgkin's communication by finger activity. The information transmission equipment prepared by the wearable triboelectric nano-generator comprises a glove and a touch electrode, wherein the glove is prepared by adopting a first friction layer, and the touch electrode is prepared by adopting a second friction layer. It can be understood that when the glove is worn on the hand of the user, the user can contact the touch electrode through the glove to output a corresponding signal, and communication is achieved.

In order to realize more complex information output, a first friction layer can be arranged on two or two fingers of the glove respectively, and each finger provided with the first friction layer can be used as a signal output source, so that more complex signal output is realized.

Fig. 5 is a schematic diagram of output signals of an information transmission device according to an embodiment of the present application, as shown in fig. 5, the embodiment includes 5 signal output sources (each solid line represents one signal output source, corresponding to five fingers on a glove), and combinations between the signal output sources are used to represent different information outputs. For example, if five solid lines are respectively used as the first signal output source, the second signal output source, the third signal output source, the fourth signal output source and the fifth signal output source from bottom to top, when there is signal output from the first signal output source and there is no signal output from the other signal output sources, the output signal is 10000; when the fourth signal output source and the fifth signal output source have signal output and other signal output sources do not have signal output, the output signal is 00011; when the first signal output source and the third signal output source have signal output and other signal output sources have no signal output, the output signal is 10100. The wearable triboelectric nano generator can realize real-time communication, so that the electronic communication technology is more convenient. Of course, other definitions can be made for the output signal by those skilled in the art, and the embodiment of the present application does not limit this.

In addition, the friction layers on the glove and the touch electrode can be interchanged, for example, the glove is provided with a second friction layer, and the touch electrode is provided with a first friction layer.

Unlike rigid connections of conventional electronic devices, flexible electronic devices are prone to introduce contact resistance during use. For resistive sensors, when contact resistance is introduced, it can result in abnormal signal output. In a breath detection device, the life safety of the monitored patient is seriously threatened. Fig. 6 is a schematic diagram of an output voltage signal before and after a resistive sensor introduces a contact Resistance, as shown in fig. 6, after the resistive sensor introduces the contact Resistance (Resistance induced), a Threshold (Threshold) is caused to be lower than the output signal as a whole. In this case, the output signal is continuously greater than the threshold, and the system will not alarm even without a respiratory signal.

However, the device prepared based on the wearable triboelectric nanogenerator provided by the embodiment of the application has higher application reliability of the self-powered sensor in the flexible circuit compared with a resistive sensor because the open-circuit voltage is not interfered by the additional resistance in the circuit. Fig. 7 is a schematic diagram of output voltage signals before and after the wearable triboelectric nanogenerator introduces contact resistance, as shown in fig. 7, before and after the contact resistance is introduced, the output signal changes little, and normal monitoring can be performed.

It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The same and similar parts in the various embodiments in this specification may be referred to each other. Especially, for the terminal embodiment, since it is basically similar to the method embodiment, the description is relatively simple, and the relevant points can be referred to the description in the method embodiment.

The above-described embodiments of the present application do not limit the scope of the present application.