WO2018045980A1

WO2018045980A1 - Deformable flexible nano generator and manufacturing method therefor, sensor and robot

Info

Publication number: WO2018045980A1
Application number: PCT/CN2017/100882
Authority: WO
Inventors: 赖盈至; 邓佳楠; 文震; 王中林
Original assignee: 北京纳米能源与系统研究所
Priority date: 2016-09-08
Filing date: 2017-09-07
Publication date: 2018-03-15

Abstract

A deformable flexible nano generator and a manufacturing method therefor, a sensor and a robot. The deformable flexible nano generator provided herein comprises: a flexible packaging structure (1) and an electrode (2) embedded in the flexible packaging structure, wherein the electrode (2) is a patterned electrode formed by the aggregation of a nano material; the flexible packaging structure (1) adopts a stretchable elastic packaging material. The deformable flexible nano generator can be stretched and deformed in biaxial directions, and can be attached to a surface of a regular or irregular object to operate; the flexible nano generator can achieve complex deformations such as stretching, bending, twisting and the like, and can withstand a great deal of mechanical deformations and damages; when attached to an irregular or regular object, the present invention may convert energy generated by induction or contact friction with the other object into electrical energy, and output the same. A flexible sensor having the flexible nano generator may be applied in the field of wearable devices; by means of electrical signals generated by the flexible sensor, a flexible robot may sense movements, working conditions, environment and external stimulations thereof.

Description

Deformable flexible nanogenerator, preparation method thereof, sensor and robot

Technical field

The invention relates to the field of generators, in particular to a deformable flexible nanogenerator, a preparation method thereof, a sensor and a robot.

Background technique

Since 2012, the nano-generator system based on electrostatic induction friction effect has been extensively researched and developed. Some efficient and stable devices and technologies have been developed, which provides a new thinking and guidance for new energy sources. However, since the generator needs to be in contact with or rubbed against other materials to work, the devices of the current friction nano-generator are mainly rigid structures and cannot be bent, stretched or deformed at will. This feature inevitably imposes a large limitation on the application of nano-generators, making it impossible to implement widely on irregular objects or wearable fields.

With special deformation capabilities, such as flexible, easy to fold, pullable electronic components have been greatly concerned by academic and industrial researchers, and is considered to be the next generation of electronic devices. This deformable electronic device has a large degree of freedom in application, and thus can be used in a wider range of applications in the field of smart devices and sensors. For example, the electronic devices can be evenly covered on irregular, soft, unfixed objects and even organs, and are widely used in the fields of wearable electronics, bio-portable systems, personal safety, robotic man-machine docking, and electronic skin. The future of the application. Although many deformable electronic devices have been widely prepared and studied before, reliable output power is still one of the most critical and important issues at present.

Recently, friction nanogenerators (TENG) have successfully demonstrated the ability to convert ubiquitous mechanical energy into electrical energy. TENG which can be bent and pulled to a certain extent by using a tantalum electrode array and a wavy polyimide film has been reported. However, the TENG is made of a rigid material, which limits its pulling characteristics and cannot be folded or complicatedly deformed multiple times, which will seriously affect the development and research of energy materials in the new wearable field. In addition, in practical applications, the nano-generator is connected to the flexible deformable device. Due to the mismatch of Young's modulus, there is a problem of unstable adhesion at the joint of the rigid material and the flexible material.

Summary of the invention

(1) Technical problems to be solved

In view of the above problems, the present invention provides a deformable flexible nanogenerator, which is prepared The method, sensor and robot make the flexible nano-generator can realize complex deformation such as pulling, bending and torsion, and can withstand great mechanical deformation and damage, attach it to regular or irregular objects, and other objects. The energy generated by contact friction and induction is converted into electrical energy output.

(2) Technical plan

According to an aspect of the present invention, a deformable flexible nanogenerator includes a flexible package structure and an electrode embedded in the flexible package structure, wherein the electrode is a pattern electrode formed by aggregation of nano conductive materials; The structure is prepared using a stretchable elastomeric encapsulating material.

Preferably, the electrode is connected to a ground, an equipotential or an external electrical conductor, and during the contact separation of the object from the flexible package structure, a charge flows between the electrode and the ground or an equipotential.

Preferably, the external electrical conductor is a human body or a copper electrode.

Preferably, the deformable flexible nanogenerator comprises a plurality of said electrodes.

Preferably, a plurality of said electrodes are respectively connected to ground, equipotential or external electrical conductors.

Preferably, the plurality of electrodes are arranged in an array.

Preferably, the nano-conductive material comprises carbon nanotubes, carbon residue, metal nanowires or metal particles or metal fragments.

Preferably, the nano-conductive material is a silver nanowire having a diameter of 100 nm to 10 μm and a length of 20-50 μm.

Preferably, the material of the flexible packaging structure comprises silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy resin or Eco-flex.

Preferably, the flexible nanogenerator has a thickness of 500 nm to 1 cm.

Preferably, the electrode is embedded in the package structure by pouring an elastic encapsulation material on the pattern electrode.

According to another aspect of the present invention, a flexible sensor comprising the nanogenerator of any of the above is provided.

Preferably, the deformable flexible nanogenerator is attached to a regular or irregular surface of the object to work.

According to still another aspect of the present invention, a method for preparing a deformable flexible nanogenerator is provided, including the steps of:

A0, pouring a solution composed of a nano conductive material into the drawn electrode pattern mold, After drying, a pattern electrode of a nano conductive material is obtained;

A1, a gel formulated from a material of a flexible package structure is cast and encapsulated on the pattern electrode of the nano-conductive material, and cured.

Preferably, the step A1 includes:

Casting the gel prepared from the flexible encapsulating material to one side of the pattern electrode of the nano-conductive material, such that the pattern electrode of the nano-conductive material is embedded in the flexible encapsulating material, and curing; the nano-conductive material is One end of the electrode is connected to the ground, an equipotential or an external conductor by a wire;

Casting the gel formulated from the flexible encapsulating material onto the other side of the pattern electrode of the nano-conductive material such that the pattern electrode of the nano-conductive material is encapsulated in the flexible encapsulating material, and the cured body is obtained Deformable flexible nanogenerator.

Preferably, the gel of the flexible encapsulating material comprises: mixing the two solutions of Eco-flex A and B in a volume ratio of 1:1 to obtain a gel of a flexible encapsulating structural material.

Preferably, the nano-conductive material comprises carbon carbon nanotubes, carbon residue, metal nanowires, metal particles or metal fragments.

Preferably, the flexible encapsulating material comprises silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy resin or Eco-flex.

Preferably, the thickness of the flexible encapsulating material on one side is 400 nm to 2 mm; and the thickness of the flexible nanogenerator obtained after curing is 500 nm to 1 cm.

According to still another aspect of the present invention, the present invention also provides an autonomously aware flexible robot comprising: a robot component; a flexible sensor attached to the robot component; wherein the flexible sensor comprises a flexible package structure and embedded in the flexible An electrode in a package structure, wherein the electrode is connected to a ground, an equipotential or an external electrical conductor.

Preferably, a flexible microstructure modifying layer having a pattern is further disposed on the surface of the flexible package structure.

Preferably, the surface of the flexible microstructure modifying layer is an array formed by pyramid-shaped microstructure units, or an array formed by microstructure units composed of nanowire clusters, or an array formed by trapezoidal shaped micro-structure units.

Preferably, the size of the microstructure unit in the array ranges from micrometer to millimeter; and/or the height of the microstructure unit in the direction of the surface of the vertical microstructure modification layer in the array is micro Meter to millimeter.

Preferably, the autonomously aware flexible robot further comprises a signal generating component, wherein the signal generating component is coupled to the flexible sensor to convert the electrical signal of the flexible sensor into other signals; preferably, the signal generating component is an LED light.

Preferably, the robot component is a crawler robot component comprising a plurality of pneumatic chambers.

Preferably, the flexible sensor is disposed on the abdomen or back of the crawling robot component.

Preferably, one of the flexible sensors is disposed on the abdomen at a corresponding position of the first stage of the crawler robot component.

The application of the autonomously aware flexible robot in pulse sensing.

The application of the autonomously aware flexible robot in touch sensing, wherein the flexible sensor is disposed on the back of the crawling robot component.

Preferably, the robot component is a robotic gripper, and the flexible sensor is disposed on two fingers of the robotic gripper.

Preferably, the robot component is a machine finger and the flexible sensor is disposed on a machine finger.

The application of the autonomously aware flexible robot in humidity or temperature sensing.

(3) Beneficial effects

It can be seen from the above technical solutions that the deformable flexible nano-generator provided by the invention, the preparation method thereof, the sensor and the robot have the following beneficial effects:

By using nano-conducting materials to form electrodes and using a stretchable elastic material to make a flexible package structure, the deformable flexible nano-generator itself has full flexibility and pullability, and can be stretched in a biaxial direction and adapted to various shapes of objects. It can realize complex deformation such as pulling, bending, twisting, folding, etc., and can be attached to regular or irregular objects, and can even withstand great mechanical deformation and damage, and has stable performance and durability; especially in the wearable field. It can be attached to the surface of any shape object, and it can be induced, contacted and rubbed with other objects to generate electric energy. It can be used in a wide range of applications. The flexible robot can sense its own motion, working state, environment and external by the electrical signal generated by the flexible sensor itself. Stimulate and achieve self-awareness.

DRAWINGS

FIG. 1 is a schematic structural view of a deformable flexible nano-generator provided by the present invention.

2 is a schematic structural view of a deformable flexible nanogenerator according to the present invention including a plurality of electrodes.

3 is a schematic flow chart of preparing a deformable flexible nanogenerator provided by the present invention.

4A is a schematic diagram of current output of a deformable flexible nanogenerator when deformed in the long axis direction.

4B is a schematic diagram of current output of a deformable flexible nanogenerator when deformed in the short axis direction.

Figure 5 is a schematic diagram of current output of a deformable flexible nanogenerator in the event of torsional deformation.

Figure 6 is a schematic diagram of current output of a deformable flexible nanogenerator in the event of folding deformation.

7 is a schematic diagram of current output of a deformable flexible nanogenerator in the event of shear damage or simultaneous shear damage and tensile strain.

FIG. 8 is a schematic structural view of a first embodiment of a self-aware flexible robot according to the present invention.

FIG. 9 is a schematic structural view of a second embodiment of a self-aware flexible robot according to the present invention.

10 and FIG. 16 are schematic structural views of a third embodiment of a self-aware flexible robot according to the present invention.

11 to 13 are test results of the flexible sensor of the third embodiment.

FIG. 14 is a schematic structural view of a fourth embodiment of a self-aware flexible robot according to the present invention.

Figure 15 is a test result of the flexible sensor of the fourth embodiment.

FIG. 17 is a schematic structural view of a fifth embodiment of a self-aware flexible robot according to the present invention.

Figure 18 is a test result of the flexible sensor of the fifth embodiment.

【Symbol Description】

1-package structure; 2,201,202,...,209-electrode;

3-ground / equipotential / external conductor; 4-current recording or sensor device;

10-robot component; 20-flexible package structure;

30-electrode; 40-metal conductor;

50-ground, equipotential or external conductor; 60-microstructured layer;

70-object; 80-baby pants;

11-crawling robot parts; 21, 22, 23, 24-flexible sensors;

12, 13 - robot parts; 14 - machine fingers.

detailed description

The invention provides a deformable flexible nano-generator, a preparation method thereof and a sensor, which are formed by using a nano-conductive material to form an electrode and a stretchable elastic material to form a flexible package. The structure makes the deformable flexible nano-generator itself fully flexible and stretchable, can be stretched in the biaxial direction and adapt to various shapes of objects, and can realize complex deformation such as pulling, bending, twisting, etc., and can be attached to the rule. Or on irregular objects, even with extreme mechanical deformation and damage, stable performance and durability.

The present invention will be further described in detail below with reference to the specific embodiments of the invention.

It should be noted that in the drawings or the description of the specification, the same reference numerals are used for similar or identical parts. Moreover, in the drawings, the shape or thickness of the embodiment may be expanded and simplified or conveniently indicated. Furthermore, elements or implementations not shown or described in the figures are in the form known to those of ordinary skill in the art. Additionally, although an example of a parameter containing a particular value may be provided herein, it should be understood that the parameter need not be exactly equal to the corresponding value, but rather may approximate the corresponding value within an acceptable tolerance or design constraint.

The invention has invented a deformable flexible nanogenerator, a preparation method thereof and a fabricated sensor through a plurality of research experiments. A typical structure of a deformable flexible nanogenerator is shown in FIG. 1 , including a flexible package structure 1 and an electrode 2 embedded in the flexible package structure 1 , wherein the electrode 2 is a pattern electrode formed by aggregation of nano conductive materials; Preparation of a stretchable elastomeric encapsulating material.

Since the electrode is formed by aggregating nano-conducting materials and the flexible packaging structure is made of a stretchable elastic material, the deformable flexible nano-generator itself has full flexibility and pullability, and can be stretched in a biaxial direction and adapted to various shapes and objects. Especially in the wearable field, it can be attached to the surface of any shape object, and it can induce, contact and rub against other objects to generate electric energy.

The electrode 2 can be connected to the ground, equipotential or external conductor 3, and during the contact separation of the other object from the flexible package structure 1, there is a charge flow between the electrode and the ground or the equipotential. The generator principle of the deformable flexible nanogenerator is a single-electrode mode, that is, the friction between the other objects outside the nano-generator and the material surface of the package structure 1 generates a charge on the surface of the package structure 1, so that the internal electrode 2 induces the opposite The electric charge can be directionally moved between the electrode 2 and the ground 3 through the rectifying member to form a current output to realize power generation.

The external electrical conductor can be a human body or a copper electrode, and the flexible nano-generator of the present invention can be attached to a movable part such as a human joint, and the energy for collecting the human body motion is converted into electric energy.

The nano conductive material of the electrode of the flexible nanogenerator of the present invention may be silver nanowire, carbon nano Rice tubes, carbon residue, metal nanowires, metal particles or metal fragments; the material of the flexible packaging structure may be silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy resin or Eco-flex.

The electrode 2 is embedded in the package structure 1 by pouring an elastic encapsulating material on the pattern electrode to ensure better bonding between the two, and problems such as falling off of the electrode do not occur.

The deformable flexible nanogenerator of the present invention can be used as a flexible sensor that is attached to a regular or irregular surface of the object for sensing whether the object is contacted or the like.

Specifically, the method for preparing a deformable flexible nano-generator provided by the present invention comprises the steps of: A0, pouring a solution prepared from a nano-conductive material into a drawn electrode pattern mold, and drying to obtain a nano-conductive material pattern electrode; A1. A gel cast from a flexible encapsulating material is encapsulated on the nano-conductive material pattern electrode and cured.

In the above method, the gel of the flexible encapsulating material comprises: mixing the two solutions of Eco-flex A and B in a volume ratio of 1:1 to obtain a gel of a flexible encapsulating material.

It should be noted that Eco-flex is a series of products of SMOOTH ON Company of the United States. The two solutions A and B are AB mixed materials of ECO FLEX products, which can form silicone rubber after mixing.

In the above method, the nano conductive material may be silver nanowires, carbon nanotubes, carbon residue or metal nanowires, metal particles or metal fragments, and the like. The flexible encapsulating material may be a flexible stretchable material such as silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy resin or Eco-flex.

Further, the A1 specifically includes: casting a gel formulated from a flexible packaging structural material onto one side of the nano conductive material to form a patterned electrode, such that a pattern electrode of the nano conductive material is embedded in the flexible package In the structural material; the flexible packaging material has a thickness of 400 nm to 2 mm after curing; one end of the patterned electrode of the nano conductive material is connected to the copper electrode with silver glue; and the gel prepared from the flexible packaging material is poured on the gel The other side of the pattern electrode of the nano-conductive material is such that the pattern electrode of the nano-conductive material is encapsulated in the flexible packaging material; the flexible nano-generator obtained after curing has a thickness of 500 nm to 1 cm.

The most prominent advantage of the deformable flexible nanogenerator provided by the present invention is that the power generating device is fully flexible and all parts of the generator can be deformed or stretched.

Because nano-conductive materials such as silver nanowires have high conductivity, pullability, low power consumption and easy For the advantages of preparation, we use materials such as silver nanowires as the conductive medium. Nano-conducting materials such as silver nanowires are stacked together and intertwined to form a conductive network. One-dimensional materials such as silver nanowires are cross-linked by one-way materials mainly by means of permeation networks. This method can prevent conductive Sexual conditions quickly adapt to various stresses and deformations.

Another key material in the present invention is the use of a flexible encapsulating material such as a soft and tough silicone rubber material as a dielectric material and used to seal the nano-conductive material. Silicone rubber and other materials have strong pullability and fracture resistance, so that a one-dimensional material of nano-conductive material is encapsulated in the material of the flexible package structure to prepare a stretchable flexible nano-generator device, which can be attached with different The shape of the object is changed or pulled, and it can work normally in the case of simultaneous deformation in both directions. The highest shape variable can reach 300%. Moreover, the limit of its breaking is greatly improved. At present, the most commonly used flexible materials for nano-generators have poor tensile properties and low strength, and are easily broken after being stressed.

The second advantage of the deformable flexible nanogenerator provided by the present invention is that the device has damage tolerance. Unlike other rigid nano power generation devices, when the nano-generator is subjected to external stress, part or even most of the device itself is damaged. As long as the electrode has a small number of connections, the device can still work normally and continue to provide energy for other devices, which greatly enhances its application value and potential.

In terms of raw materials and preparation processes, the flexible encapsulating material such as silicone rubber used in the invention has low cost and simple production process, and only needs to be prepared by a dissolution method at room temperature, the operation is simple, the production environment is low, and the production cost is greatly reduced. Suitable for mass production.

In summary, the deformable flexible nanogenerator of the present invention is characterized by both mechanical durability and elasticity, with ultra-high biaxial pull characteristics and the ability to generate energy under different extreme deformation conditions. This new type of nanogenerator can be applied and adapted to a variety of irregular objects such as human skin, spheres, tubes and irregular shapes, etc., and is also used as an energy source to power other electronic devices. Because the flexible nanogenerator itself has the pullability and durability, it can generate electricity by tapping and contact under different deformation conditions. At the same time, its biaxial stretching can exceed 300%, and even in the extreme case of damage, the device can still work normally to provide energy for the load.

In addition, current prototype devices have been demonstrated to drive a commercial smartwatch while enabling self-powered electronic skin array detection without the need for external energy support.

In the above embodiment, the deformable flexible nanogenerator includes only one electrode, and is implemented in other implementations. In the example, the deformable flexible nano-generator may also comprise a plurality of electrodes. Referring to FIG. 2, the plurality of electrodes may be respectively connected to the ground, the equipotential or the external conductor, or each electrode may be connected to the same one through the rectifying device. Ground potential.

When used as a sensor, the plurality of

electrodes

201, 202, ... 209, etc. are respectively connected to ground, equipotential or external conductors, and the plurality of

electrodes

201, 202, ... 209, etc. may be arrayed. Way distribution. A current recording or sensing device 4 can be connected between the electrode 201 and the ground potential 3. When the position of the electrode 201 is touched or tapped, an electrical signal is output, and the current recording or sensing device 4 can be used for recording or recording of the sensor member. Current between 201 and ground potential 3. If the current recording or sensor device 4 is connected between each electrode and the ground potential 3, the different electrode positions are touched or tapped, and the touched position can be known according to the current recording or the operation of the sensor device 4 as a sensor to sense The touch situation of different positions realizes multi-zone sensing, and in the future practical application, it can be made into the skin of the robot to sense the external force.

The technical solution of the present invention will be described below with a specific embodiment.

It should be noted that this embodiment is only for understanding the present invention and is not intended to limit the scope of the present invention. Moreover, the features in the embodiments are applicable to the method embodiments and the device embodiments at the same time, and the technical features appearing in the same or different embodiments can be used in combination without conflicting with each other. .

The nano conductive material of the electrode of the flexible nanogenerator of the present invention may be silver nanowire, carbon nanotube, carbon residue, metal nanowire, metal particle or metal fragment, etc.; the material of the flexible packaging structure may be silicone rubber, silica gel, rubber , polydimethylsiloxane, epoxy resin or Eco-flex. Since the performance of each type is relatively similar, the present embodiment only uses one material for explanation, and does not enumerate one by one.

A schematic diagram of the preparation process is shown in FIG.

The silver nanowires were from Sigma-Aldrich, having a diameter of about 115 nm (optional range 100 nm to 10 μm), a length of 20-50 μm, and a formulation concentration of 0.05% by weight. Using an acrylic plate as a substrate, the surface was first cleaned and the desired electrode pattern was drawn, and then the drawn electrode pattern was processed with a polyimide tape to obtain an electrode template. Next, the prepared silver nanowire solution was dropped into the template, and after it was completely dried at room temperature, the polyimide tape was removed to obtain a silver nanowire pattern electrode.

It should be noted that the concentration of the silver nanowire solution is not particularly limited. The concentration given in the examples is only for the nanowires to not aggregate, but the concentration is low or high, which only affects the production time. Between, the concentration is high, the production is fast; if the concentration is low, the production is slow. The concentration is lower, the material is more economical, and it will be more uniform.

A silicone rubber gel was then prepared. The silicone rubber was from Smooth-On, model Eco-flex00-10. The two solutions A and B were thoroughly mixed in a volume ratio of 1:1, and then the mixed gel was cast on an acrylic plate with a silver nanowire electrode pattern to a thickness of about 2 mm (optional range 400 nm to 2 mm). The silicone rubber gel is completely cured after 4 hours at room temperature, and then the silicone rubber is peeled off from the acrylic plate, and the silver nanowire electrode pattern has been embedded in the silicone rubber. It is then connected to the ground electrode by a copper wire at the end of the silver nanowire pattern, and the two are connected by silver glue. After the test is conducted, the silver nanowire electrode is again encapsulated with a silicone rubber gel, and the thickness after packaging is about 4 mm (optional range: 500 nm to 1 cm) to form a sandwich structure in which the silver nanowire pattern electrode is embedded in the silicone rubber. After curing again for 4 hours at room temperature, the desired deformable flexible nanogenerator was obtained.

The working mechanism is mainly based on electrostatic induction and triboelectric charging. When the skin is in contact with silicone rubber, the electrons will flow from the skin to the silicone rubber when the two are in contact, when the two are in contact. The negative charge on the surface of the silicone rubber will induce a positive charge on the intermediate silver nanowire pattern electrode interlayer, causing electrons to flow from the silver nanowire electrode interlayer to the ground direction. This electrostatic induction process can provide a voltage/current signal to the external load. Output. When the distance between the skin and the silicone rubber is increased, the negative triboelectric charge on the surface of the silicone rubber is completely shielded by the positive charge of the silver nanowire electrode, and there is no signal output at this time. When the distance between the skin and the silicone rubber is reduced to the full contact process, the induced positive charge in the silver nanowire electrode will decrease, and the electron flow direction is from the ground to the silver nanowire electrode, again forming a reverse voltage. / Current signal output.

The formed nano-generator device has good tensile properties and can work normally under extreme mechanical deformation, such as stretching and folding, and can still work normally even in the case of large-area damage of the device, the input will not There is a significant change, even when the device is pulled, the device output will become larger. As shown in Figures 4A and 4B, the maximum tensile strain of the device in the biaxial direction can reach 300%, or as shown in Figure 5. Torsing at different angles, or as shown in Figure 6, can be folded multiple times, or as shown in Figure 7, shear damage or shear damage and tensile strain can still output a strong electrical signal, current density up to mA Every cubic meter.

The invention also proposes to use the above deformable flexible nano-generator as a flexible sensor, placed in a component of the flexible robot, and realize the autonomous perception of the flexible robot.

The self-aware flexible robot will be described below with reference to specific embodiments.

Embodiment 1:

FIG. 8 is a schematic diagram showing a typical structure of an autonomously-aware flexible robot according to the present embodiment. As shown in FIG. 8, the autonomously-aware flexible robot includes a robot component 10 and a flexible sensor attached to the robot component 10, wherein the robot component 10 can be Various actions are performed under the driving of the driving device, such as moving, gripping objects, crawling, etc.; the flexible sensor comprises a flexible package structure 20 and an electrode 30 embedded in the flexible package structure 20, wherein the electrode 30 can be connected to the ground, equipotential Or the external electrical conductor 50, under the action of the action of the robot component 10, when the flexible packaging structure 20 is in contact with or separated from other objects, due to frictional electrification and electrostatic induction, there is a relationship between the electrode 30 and the ground or the equipotential. The charge flows, and different actions can produce different electrical signals. Therefore, the generated electrical signal can be used as a signal that the flexible robot autonomously perceives, and does not need to supply power to the sensor, and is an autonomously aware flexible robot.

Preferably, the electrode 30 can be connected to an electrical conductor disposed on the robot component 10.

The electrode 30 can be any conductive material. In order to make the flexible triboelectric sensor have better flexibility and reliability, the electrode 30 can be an electrode formed by aggregating the nano conductive material, and the shape and size of the electrode can be designed according to the required pattern. Make special restrictions.

The flexible package structure 20 adopts a stretchable elastic packaging material, so that the flexible frictional electric sensor itself has full flexibility and pullability, can be stretched in the biaxial direction, and can adapt to the conductive action of various robot components and closely fits the robot component. On any surface of the shape, it induces, contacts and rubs against other objects to generate an electrical signal that is fed back to the control system of the robot component.

The nano conductive material of the electrode 30 may be silver nanowires, carbon nanotubes, carbon residue, metal nanowires, metal particles or metal fragments, etc.; the material of the flexible package structure 10 may be silicone rubber, silica gel, rubber, polydimethylsiloxane. Organic insulating materials such as oxane, epoxy resin or Eco-flex.

For the case where the electrode 30 is made of a nano-conductive material, it can be connected to the ground 50 by a metal conductor 40 that protrudes from the flexible package structure 10.

The flexible sensor is prepared by pouring a solution prepared from a nano conductive material into a drawn electrode pattern mold, and drying to obtain a nano conductive material pattern electrode; and molding a gel prepared from a flexible packaging material into the nanometer. The conductive material is patterned on the electrode and cured.

Embodiment 2:

In the present embodiment, a typical structural diagram of an autonomously-aware flexible robot is shown in FIG. 9, which is different from the autonomously-aware flexible robot in the first embodiment: a flexible triboelectric sensor In addition to the flexible package structure 20 and the electrodes 30 embedded in the flexible package structure 20, a flexible microstructure modification layer 60 having a pattern is disposed on the surface of the flexible package structure 20. The microstructured layer 60 can be deformed when the flexible triboelectric sensor is stressed or touched, and the charge induced on the electrode 30 can change due to frictional electrification and electrostatic induction, and the pressure or touch can be sensed.

The material of the microstructure modifying layer 60 is made of a flexible deformable insulating material, preferably an organic insulating material, and may be an organic insulating material such as silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy resin or Eco-flex. The material of the microstructure modifying layer 60 may be the same as or different from the material of the flexible package structure 20, and may be integrally formed with the flexible package structure 20, or the microstructure modifying layer 60 may be attached to the surface of the flexible package structure 20. As shown in FIG. 9, the surface of the microstructure-modifying layer 60 may be an array formed of pyramid-shaped microstructure units, or an array formed of microstructure units composed of nanowire clusters, or an array formed of trapezoidal-frame shape microstructure units. The size of the microstructure units in the array ranges from micrometers to millimeters, for example from 50 micrometers to 500 micrometers; the height of the microstructure units in the array in the direction of the surface of the vertical microstructure modification layer 50 ranges from micrometers to millimeters, for example 50 Micron to 500 microns.

A flexible device having a pyramidal triangular microprism surface has excellent pressure sensitivity of low pressure (<5 kPa) even when stretched to 100% strain.

The preparation process of the flexible sensor is described by a specific example. A pyramid-shaped array of dies was fabricated on an acrylic plate using a laser cutter. A silicone rubber solution of Eco-flex 00-30 (from Smooth-On Co., model Ecoflex 00-30) was mixed at a weight ratio of 1:1 Part A and Part B solution, and the mixed solution was poured into the above mold. After 4 hours, the silicone rubber film of the top layer having the array of triangular prism elements was cured and peeled off to obtain a microstructure-modifying layer 60. The mixed silicone rubber solution was poured onto an acrylic plate which was pre-drop coated with silver chips (size about 10 μm, purity ≥99.9%) and had a boundary. After curing, the film was peeled off to obtain a strip-like sheet in which silver chips were embedded in the silicone rubber, and then the conductive copper tape was joined and embedded in the substrate of the strip-like sheet, and joined to the silver chips. The two sheets of the silicone rubber film obtained above were pasted with a silicone rubber solution to form a flexible sensor of the structure shown in FIG.

Embodiment 3:

In this embodiment, an autonomously aware flexible robot is provided, wherein the robot component is a three-stage crawling robot component 11 including three pneumatic chambers as shown in FIG. The robotic component is preferably a flexible structure that can be crawled on any surface, and the crawling robot can be controlled to move, particularly to a dangerous place, such as a pneumatic robot that can crawl on the surface of the object 70. The flexible robot may include one or more flexible sensors 21 provided on the abdomen (the side on which the surface of the object 7 crawls) or the back of the crawling robot part 11.

In this embodiment, the crawling robot component 11 is a three-stage structure of three pneumatic chambers, and specifically includes several pneumatic chambers, which should not limit the protection range of the present invention, and may be more segments in other embodiments.

The process of manufacturing a crawler robot component can be referred to (Elastomeric Origami: Programmable Paper-Elastomer Composites as Pneumatic Actuators, Adv. Funct. Mater. 2012, 22, 1376-1384). The mold comprises three parts: 1. The bottom layer; 2. The pneumatic chamber ; 3, integrated mold. For the bottom layer, a piece of paper was embedded in the formed 1/16 inch thick Eco-flex 00-30 silicone rubber film. The pneumatic chamber was obtained by Eco-flex 00-30 which was solidified in the relevant mold. The Eco-flex pneumatic chamber is adhered to the bottom layer for assembly. After that, the pneumatic chamber is inverted in a larger integrated mold. The mixed Eco-flex 00-30 was poured into an integrated mold and assembled with the prefabricated deformable flexible sensor of Example 2. After four hours, the silicone rubber is solidified, and a flexible robot with crawling ability is integrally formed.

In the flexible robot of FIG. 10, only one flexible sensor is disposed on the abdomen of the corresponding position of the first-stage pneumatic chamber of the leftmost end of the crawling robot component 11, and the crawling robot crawls back and forth from the left side to the right side of the crawling robot, at the electrode and The output electrical signal between the grounds, Figure 11 shows the gait electrical signal (Normalized V) output produced by the crawler robot component 11 moving a distance of about 15 cm, showing several cycles of the generated potential wave. Each period of the electrical signal curve corresponds to a volt gait. Figure 12 shows a detailed electrical signal (Normalized V) output for a wave of gait.

As can be seen from Figures 11 and 12, the output changes as the pneumatic actuator of each pneumatic robot component moves. When the leftmost first segment initiates an expansion bend, the potential is at its lowest state. This result is due to the first segment bending resulting in separation between the flexible sensor and the surface of the object 70. When the first segment is deflated and close to the object 70, the generated voltage rises. When the first segment contacts the object 70, the output reaches a high voltage state. When the third segment expands, the potential reaches its maximum value. This result is due to the application of more force on the flexible sensor on the first segment during the third segment of inflation. Potential, deflated the third segment, and the second segment expanded, the potential slightly decreased. When the third section is completely emptied and the second end is expanded, the potential generated rises again. When the first segment is re-inflated When the potential drops again to the lowest value. These results indicate that a conscious aerodynamic robot component can actively perceive its crawling state.

The soft body of the crawlable pneumatic robotic component enables it to adaptively connect itself to a regular or irregular surface of the object for sensing and providing a safer way of use. To demonstrate this ability, a crawlable pneumatic robotic component is controlled to crawl an irregular surface and crawl to the human wrist, touching the human wrist and sensing the pulse to actively sense a slight human physiological signal. Figure 13 shows the pulse signal of the human wrist detected by the flexible sensor, illustrating the potential of the self-consciously aware flexible robot in in situ medical palpation and other medical applications.

The working mechanism of the flexible sensor is mainly based on the contact frictional electrification and electrostatic induction when it is in contact with other materials. Since the electron affinity of the skin and the silicone rubber are different, the electrons will flow from the skin to the silicone rubber when the two are in contact. The negative charge on the surface of the silicone rubber will induce a positive charge on the intermediate silver nanowire electrode interlayer, causing electrons to flow from the silver nanowire electrode interlayer to the ground direction. The electrostatic induction process provides an output of the voltage/current signal to an external load. When the distance between the skin and the silicone rubber is increased, the negative triboelectric charge on the surface of the silicone rubber is completely shielded by the positive charge of the silver nanowire network, and there is no signal output at this time. When the distance between the skin and the silicone rubber is reduced again to the complete release process, the induced positive charge in the silver nanowire network will decrease, and the electron flow direction will be from the ground to the silver nanowire, again forming a reverse voltage / Current signal output.

The flexible robot may further include a signal generating component, and the signal generating component may be connected to the flexible sensor. For example, the signal generating component may be a device such as an LED or the like, and may convert the electrical signal of the flexible sensor into other signals such as light, sound, and the like. People or machines interact. As shown in FIG. 16, by integrating the flexible sensor in a plurality of areas, the robot component 12 actively performs multiple sensing when it moves, such as crawling, and can also interact with a person, and can be used as an integrated robot crawler. The robotic component 12 is constructed from three pneumatic chamber sections, and each pneumatic chamber back is integrated with a flexible sensor. As the active skin, the three flexible sensors 22 can not only sense the movement of the attached robot components (similar to muscle movement), but also serve as an autonomous human-computer interaction interface. When a finger touches the deformed flexible triboelectric robot, it can generate electric energy. The power of the electrical energy can illuminate the LED and provide a human-visible response to interact with the outside world. Figure 11 shows an electrically driven LED produced by robot motion. The above results show that the flexible triboelectric sensor using self-generating enables the flexible robot to instantaneously communicate with people through optical signals without the need for an external power source.

Embodiment 4:

Referring to Figure 14, an autonomously aware flexible robot wherein the robotic component 13 is a conscious robotic gripper and the flexible sensor 23 is integrally integrated with the two fingers of the robotic gripper. Taking the hand of a flexible robot to grasp and raise a baby doll as an example, Figure 15 shows the use of a clamp with a flexible active sensor for holding and shaking the baby doll's hand and testing its output, initially, the left and right sensors ( Both the Left sensor and the Right sensor are in a low voltage state (initial). As the robot approaches the approach, the voltage generated by the two sensors begins to rise. These two potentials reach a maximum until they contact and compress the object. When the robot gripper grips the arm up and down, the two outputs drop slightly and remain at a lower voltage. A slight drop in output can be attributed to the contribution of a portion of the potential from the electrostatic field to the desktop. When the arm is suddenly released from the robot gripper, the response is further reduced. When this happens, the outputs of the two sensors drop dramatically to a minimum in an instant. The results in the figure show that when the robot gripper grips the hand, the resulting voltage is slightly reduced. When the robot gripper shakes hands, the generated potential responds to the action accordingly. After the robot gripper releases the hand, the output returns to the baseline value. The results show that different potentials allow conscious robotic grippers to feel the different movements of the object and to be aware of the fall off accident.

Embodiment 5:

When the flexible triboelectric sensor is touched or squeezed, the ambient temperature, humidity, and the like have an influence on the output signal. Therefore, the embodiment provides a flexible robot that can be applied to temperature or humidity sensing, and can be applied to the nursing robot. In other fields, it is possible to consciously detect whether the baby's trousers are wet.

17 is a self-aware flexible robot of the embodiment, wherein the robot component is a machine finger 14 and the flexible sensor 24 is disposed on the machine finger 14. The robot finger 14 can be moved by the robot to perform a touch or flip motion when flexible. The robot touches the baby pants 80 and tests the pants under both wet and dry conditions. Figure 18 shows the generated potentials for the two states. The higher and lower potentials represent the dry (Dry) and wet (Wet) pants, respectively. The reduced potential is attributed to the water molecules on the wet pants reducing the flexibility in the soft robot. Frictional charge of a triboelectric sensor.

In summary, the present invention provides a deformable flexible nanogenerator comprising a flexible package structure and an electrode embedded in the flexible package structure, wherein the electrodes are assembled by a nano-conductive material The patterned electrode is formed; the flexible package structure is prepared using a stretchable elastic packaging material. The invention also provides a preparation method of the deformable flexible nano-generator and a sensor comprising the same; and the above-mentioned deformable flexible nano-generator is used as a flexible sensor and is placed in a component of the flexible robot to realize Autonomous perception of flexible robots. By using nano-conducting materials to form electrodes and using a stretchable elastic material to make a flexible package structure, the deformable flexible nano-generator itself has full flexibility and pullability, and can be stretched in a biaxial direction and adapted to various shapes of objects. It can realize complex deformation such as pulling, bending, twisting, folding, etc., and can be attached to regular or irregular objects, and can even withstand great mechanical deformation and damage, and has stable performance and durability; especially in the wearable field. It can be attached to the surface of any shape object, and can generate electric energy by sensing, contacting and rubbing with other objects. It can be used in a wide range of applications. For example, a flexible robot can sense its own motion, working condition and environment through electrical signals generated from the flexible sensor itself. And external stimuli to achieve autonomous perception.

The specific embodiments of the present invention have been described in detail, and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

A deformable flexible nanogenerator, comprising: a flexible package structure and an electrode embedded in the flexible package structure, wherein

The electrode is a pattern electrode formed by aggregation of nano conductive materials;

The flexible package structure employs a stretchable elastic packaging material.
The deformable flexible nanogenerator of claim 1 wherein the deformable flexible nanogenerator comprises a plurality of the electrodes.
The deformable flexible nanogenerator according to claim 1 or 2, wherein

The electrode is connected to a ground, an equipotential or an external electrical conductor, and during the contact separation of the object from the flexible package structure, a charge flows between the electrode and the ground or an equipotential.
The deformable flexible nanogenerator according to claim 3, wherein the external electrical conductor is a human body or a copper electrode.
The deformable flexible nanogenerator according to any one of claims 2 to 4, wherein the plurality of electrodes are arranged in an array.
The deformable flexible nanogenerator according to any one of claims 1 to 5, wherein the nano-conductive material comprises: a carbon nanotube, a carbon residue, a metal nanowire, a metal particle or a metal fragment.
The deformable flexible nanogenerator according to any one of claims 1 to 6, wherein the nano conductive material is a silver nanowire, and the silver nanowire has a diameter of 100 nm to 10 μm and a length of 20-50 μm. .
The flexible flexible nanogenerator according to any one of claims 1 to 7, wherein the material of the flexible packaging structure comprises: silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy tree Ester or Eco-flex.
The deformable flexible nanogenerator according to any one of claims 1 to 8, wherein the deformable flexible nanogenerator has a thickness of 500 nm to 1 cm.
The deformable flexible nanogenerator according to any one of claims 1 to 9, wherein the electrode is embedded in the package structure by pouring an elastic encapsulating material on the pattern electrode.
A flexible sensor comprising any one of claims 1 to 10 Deformable flexible nanogenerator.
The flexible sensor of claim 11 wherein said deformable flexible nanogenerator is attached to a regular or irregular surface of the object.
A method for preparing a deformable flexible nanogenerator, comprising the steps of:

A0, pouring a solution prepared from a nano conductive material into the drawn electrode pattern mold, and drying to obtain a pattern electrode of the nano conductive material;

A1, a gel formulated from a material of a flexible package structure is cast and encapsulated on the pattern electrode of the nano-conductive material, and cured.
The preparation method according to claim 13, wherein the step A1 comprises:

Casting the gel prepared from the flexible encapsulating material to one side of the pattern electrode of the nano-conductive material, such that the pattern electrode of the nano-conductive material is embedded in the flexible encapsulating material, and curing; the nano-conductive material is One end of the electrode is connected to the ground, an equipotential or an external conductor by a wire;

Casting the gel formulated from the flexible encapsulating material onto the other side of the pattern electrode of the nano-conductive material such that the pattern electrode of the nano-conductive material is encapsulated in the flexible encapsulating material, and the cured body is obtained Deformable flexible nanogenerator.
The preparation method according to claim 14, wherein the formulating the gel from the flexible encapsulating material comprises: mixing the two solutions of Eco-flex A and B in a volume ratio of 1 : 1 to obtain a flexible package structure. Material gel.
The preparation method according to claim 14, wherein the nano-conductive material comprises: carbon carbon nanotubes, carbon residue, metal nanowires, metal particles or metal fragments.
The preparation method according to claim 14, wherein the flexible encapsulating material comprises: silicone rubber, silica gel, rubber, polydimethylsiloxane, epoxy resin or Eco-flex.
The method according to claim 14 or 15, wherein the thickness of the flexible encapsulating material on one side is 400 nm to 2 mm; and the thickness of the deformable flexible nanogenerator obtained after curing is 500 nm to 1 cm.
An autonomously aware flexible robot comprising:

Robot parts;

A flexible sensor according to any one of claims 11 or 12 attached to said robot component Above; wherein the electrode is connected to a ground, an equipotential or an external electrical conductor.
The flexible robot according to claim 19, wherein a flexible microstructure modifying layer having a pattern is further disposed on a surface of the flexible package structure.
The flexible robot according to claim 20, wherein the surface of the flexible microstructure modifying layer is an array formed by pyramid-shaped microstructure units, or an array formed of microstructure units composed of nanowire clusters, or a trapezoid An array of mesa shaped microstructure units.
The flexible robot according to claim 21, wherein the size of the microstructure unit in the array ranges from micrometer to millimeter; and/or the microstructure unit in the array is in the direction of the surface of the vertical microstructure modification layer. The height range is from micron to millimeter.
The flexible robot according to any one of claims 19 to 22, wherein the autonomously-aware flexible robot further comprises a signal generating component, the signal generating component being coupled to the flexible sensor to convert an electrical signal of the flexible sensor For other signals.
The flexible robot according to claim 23, wherein

The signal generating component is an LED lamp.
The flexible robot according to any one of claims 19 to 24, wherein the robot component is a crawling robot component including a plurality of pneumatic chambers.
The flexible robot according to claim 25, wherein the flexible sensor is disposed on an abdomen or a back of the crawling robot component.
The flexible robot according to claim 25, wherein one of said flexible sensors is disposed at an abdomen at a corresponding position of the first stage of the pneumatic chamber of the crawling robot member.
The use of a flexible robot according to claim 27 in pulse sensing.
The use of a flexible robot according to claim 26 in touch sensing, characterized in that the flexible sensor is disposed at the back of the crawler robot component.
The flexible robot according to any one of claims 19 to 24, wherein the robot component is a robot gripper, and the flexible sensor is disposed on two fingers of the robot gripper.
The flexible robot according to any one of claims 19 to 24, wherein the robot component is a machine finger and the flexible sensor is disposed on a machine finger.
The use of a flexible robot according to claim 31 in humidity or temperature sensing.