CN111537114A - Full nanofiber electronic skin and application device thereof - Google Patents
Full nanofiber electronic skin and application device thereof Download PDFInfo
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- CN111537114A CN111537114A CN202010333458.4A CN202010333458A CN111537114A CN 111537114 A CN111537114 A CN 111537114A CN 202010333458 A CN202010333458 A CN 202010333458A CN 111537114 A CN111537114 A CN 111537114A
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Abstract
The invention provides a full nanofiber electronic skin, which comprises an upper layer nanofiber membrane, a middle layer nanofiber membrane and a lower layer nanofiber membrane, wherein the upper layer nanofiber membrane, the middle layer nanofiber membrane and the lower layer nanofiber membrane are respectively a contact electrification layer, a middle electrode layer and a bottom supporting layer, and the contact electrification layer and the bottom supporting layer are both made of biodegradable materials; the middle electrode layer is a nanofiber membrane with a sterilization function and is electrically connected with the ground or other conductors. The electronic skin has a plurality of layers of staggered nanofiber networks and a large number of three-dimensional micro-nano hierarchical holes, so that the electronic skin has air permeability, high output and high pressure sensitivity and has antibacterial property.
Description
Technical Field
The invention relates to the field of sensors, in particular to a full-nanofiber electronic skin and an application device thereof.
Background
The human skin, as the largest organ of the human body, not only has the basic functions of protection, secretion and respiration, but also is an important somatosensory system for human perception, interaction and communication with the substance world. The development of biomimetic electronic skin has stimulated considerable interest by mimicking the features and functions of natural skin, which have wide application in wearable, personal-centric health monitoring, intelligent prosthetics, robots, human-machine interfaces, and artificial intelligence.
Electronic skin is based on different physical sensing mechanisms, such as piezoresistive, capacitive, piezoelectric and triboelectric, and is able to detect and quantify the diversity of environmental stimuli, including temperature, humidity, pressure, vibration and touch, and convert them into real-time and visible electronic impulses. The friction nano generator is a novel energy acquisition technology for converting ubiquitous mechanical energy into precious electric energy by utilizing the coupling effect of contact electrification and electrostatic induction, has the advantages of low cost, simple structure, convenience in use, various material choices, high conversion efficiency and the like, has wide application prospect in the fields of wearable power supplies and self-powered sensing, and is an ideal choice for energy-autonomous electronic skins.
Flexibility, stretchability, sensitivity, adaptability and mechanical durability are the most popular research directions for electronic skins at present and are relatively easy to implement. In recent years, special functions of electronic skins, such as recyclability, self-healing, shape memory, electroluminescence, and mechanical luminescence, have been studied in order to improve the overall performance of electronic skins. Despite the continuous optimization and perfection of the above aspects, the comfort, safety and environmental protection of electronic skins have been neglected, which largely hampers the practical application of electronic skins. Therefore, electronic skins having desirable comfort and practicality must have air permeability, biodegradability, and antibacterial properties. The air permeability is an important way for adjusting the heat-humidity balance and realizing the gas exchange between the human body and the external environment. However, most high performance electronic skins have membranes as electrodes or substrates, which may cause skin discomfort and even inflammation and itching. In addition, since the electronic skin is in long-term contact with human skin and is a good medium for the growth of microorganisms, the antibacterial property is an important property of the electronic skin for inhibiting the growth of bacteria and preventing bacterial infection. In addition, most materials are not disposable and may become electronic waste at the end of their useful life, even damaging the human body or polluting the environment.
Disclosure of Invention
The invention aims to provide a full-nanofiber electronic skin, which is based on the principle of a friction nano generator, realizes the combination of air permeability, antibacterial property, biodegradability and self-power supply of the electronic skin, and solves the problems of discomfort, bacterial infection, environmental pollution and the like of the conventional electronic skin.
In order to achieve the above object, the present invention provides an all-nanofiber electronic skin, comprising upper, middle and lower three layers of nanofiber membranes, which are respectively a contact electrification layer, a middle electrode layer and a bottom support layer, wherein,
the contact electrification layer and the bottom supporting layer are all nanofiber membranes made of biodegradable materials;
the middle electrode layer is a nanofiber membrane with a sterilization function and is electrically connected with the ground or other conductors.
Preferably, the biodegradable material comprises one or more of polyvinyl alcohol, polylactic acid-glycolic acid copolymer, polycaprolactone, polylactic acid, polyglycolic acid, polybutylene succinate, poly beta-hydroxybutyrate, polyurethane and cellulose, and can be used for preparing a high polymer material of the nanofiber by electrostatic spinning.
Preferably, the material of the middle electrode layer is silver, gold, copper nanowire or nanowire doped with silver, gold, copper nanoparticles and having a conductive function.
Preferably, the thickness of the contact electrification layer fiber film is preferably in the range of 5-120 μm; the fiber diameter range in the fiber membrane is 580-610 nm.
Preferably, the thickness of the bottom support layer is preferably in the range of 20-40 μm, and the diameter of the fibers in the fiber membrane is in the range of 120-150 nm.
Preferably, the diameter of the nanowire is in the range of 150-165.
Preferably, the contact electrification layer is made of a biodegradable material polylactic acid-glycolic acid copolymer, the middle electrode layer is made of silver nanowires, and the bottom support layer is made of a biodegradable material polyvinyl alcohol.
Correspondingly, the invention also provides an application device of the full nanofiber electronic skin, which comprises the electronic skin, wherein the electronic skin is fixed at the motion part to be detected and is used for detecting the real-time motion state of the motion part.
Preferably, the application device according to the above is a wearable device.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention provides an electronic skin composed of all nano fibers, which integrates the properties of air permeability, antibacterial property, degradability, self power supply and the like, and enriches the functions and application range of the electronic skin. The electronic skin comprises an upper layer, a middle layer and a lower layer of nanofiber membranes, wherein the upper layer is in contact with an electrification layer, a middle electrode layer and a bottom supporting layer. The electronic skin utilizes the principle of nano friction power generation, and when the electronic skin is stressed, the electrification layer and the electrode layer generate electric output in the contact and separation processes. The electronic skin has the advantages of simple structure, convenience in manufacturing, multiple functions and wide application prospect.
The upper layer electrification layer and the bottom supporting layer are all nanofiber membranes which are made of biodegradable materials through an electrostatic spinning technology, and therefore the biodegradability of the electronic skin is improved. The middle electrode layer forms a nanofiber membrane on the bottom layer through silver nanowire vacuum filtration. The silver nanowires have excellent broad-spectrum antibacterial property and endow the electronic skin with antibacterial property.
The electronic skin is provided with a plurality of layers of staggered nanofiber networks and a large number of three-dimensional micro-nano hierarchical holes, so that a high specific surface area is provided for contact electrification and pressure sensing, and a plurality of inter-fiber capillary channels are provided for heat-moisture transfer, so that the electronic skin has air permeability, high output and high pressure sensitivity.
The electronic skin application device comprises the electronic skin in the technical scheme. The application device can realize self power supply and can be used as a human body whole body physiology and motion monitoring sensing device. And the multifunctional characteristics of air permeability, antibacterial property, degradability and the like are realized, and the multifunctional antibacterial health-care pillow has a good application prospect in the aspects of personal health monitoring, patient rehabilitation, athletic performance monitoring, entertainment and activity human body motion tracking and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural view of a full nanofiber electronic skin of the present invention;
FIG. 2 is a schematic top plan view of a full nanofiber e-skin of the present invention;
FIG. 3 is a schematic view of the working principle of the full nanofiber electron skin;
FIG. 4 is a graph of output voltage, current, and charge for a particular full nanofiber electronic skin;
FIG. 5 is a graph of output voltage at different pressures for a particular full nanofiber electronic skin;
FIG. 6 shows the results of the permeability test of the full nanofiber electronic skin under different pressures;
FIG. 7 shows the results of the full nanofiber electronic skin antibacterial performance test of the present invention;
FIG. 8 shows the results of testing the degradation performance of the full nanofiber electronic skin of the present invention;
FIG. 9 is a diagram of the full nanofiber electronic skin monitoring of motion signals of human fingers and elbows at different motion angles according to the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The typical structure of the all-nanofiber electronic skin provided by the invention is shown in fig. 1 and fig. 2, and the electronic skin comprises an upper nanofiber membrane, a middle nanofiber membrane and a lower nanofiber membrane, wherein the upper nanofiber membrane is a contact electrification layer 1, a middle electrode layer 2 and a bottom support layer 3. The electronic skin utilizes the principle of a friction nano generator, and the working mode is a single-electrode working mode. When an external object, such as human skin, makes one contact and separation with the contact electrification layer 1, an alternating current signal is generated between the intermediate electrode layer 2 and the ground or other conductor connected thereto, and the continuous making of such contact and separation generates a continuous alternating current, so that the electrical skin converts mechanical energy into electrical energy. The contact electrification layer 1 and the bottom supporting layer 3 are all nanofiber membranes which are made of biodegradable materials through an electrostatic spinning technology. The middle electrode layer 2 adopts a conductive fiber membrane with a sterilization function.
In the specific preparation process, a silver nanofiber membrane serving as a middle electrode layer 2 is formed on a bottom supporting layer 3 through silver nanowire vacuum filtration, a copper foil 4 is attached to the surface of a silver nanowire serving as an extraction electrode, and then a contact electrification layer 1 is covered on the bottom supporting layer 3 with the middle electrode layer 2 through an electrostatic spinning method.
The biodegradable material used for contacting the electrification layer 1 and the bottom supporting layer 3 can comprise polyvinyl alcohol, polylactic acid-glycolic acid copolymer, polycaprolactone, polylactic acid, polyglycolic acid, polybutylene succinate, poly beta-hydroxybutyrate, polyurethane, cellulose and other high polymer materials which can be used for preparing nano fibers by electrostatic spinning.
The material of the middle electrode layer 2 may include nanowires of silver, gold, copper, etc., or nanowires doped with these nanoparticles to have a conductive function.
The properties and structure of the all-nanofiber electronic skin of the present invention are described in detail below by taking a specific electronic skin as an example. According to the structural characteristics of electronic skin, a biodegradable material polylactic acid-glycolic acid copolymer (PLGA) is used as a contact electrification layer, silver nanowires (Ag NWs) are used as a middle electrode layer, and a biodegradable material polyvinyl alcohol (PVA) is used as a bottom support layer.
The preparation process of the electronic skin comprises the following steps:
(1) and preparing the bottom supporting layer fiber membrane by an electrostatic spinning method. The optimal concentration of PVA electrostatic spinning is 10 wt%, the voltage is 25kV, the flow rate is 0.5mL/h, the diameter range of PVA nano-fiber is 120-150nm, and the preferred range of thickness is 20-40 μm.
(2) An intermediate electrode layer is prepared on the bottom support layer. The Ag NWs had a diameter in the range of 150-165nm and a length of 120 μm. The silver nanowire array is deposited on a bottom supporting layer by using a vacuum filtration method, and then a copper foil (preferably with the width of 0.5cm) is attached to the surface of the silver nanowire to be used as an extraction electrode to be connected with an external ground or other conductors for measuring the output of an electric signal.
(3) The electrostatic spinning method is used for preparing the contact electrification layer fiber membrane. The optimal concentration of PLGA electrostatic spinning is 8.5 wt%, the voltage is 15kV, the flow rate is 0.45mL/h, and the diameter of the PLGA nano fiber is about 580-610 nm. The thickness of the fiber film contacting the electrification layer can be adjusted according to the length of the spinning time, but the film is easy to damage due to the fact that the fiber film is too thin, and the middle electrode layer is easy to leak; too thick affects the air permeability and the electrification property, and the thickness is preferably in the range of 5 to 120 μm.
Fig. 3 is a schematic view of the working principle of the all-nanofiber electronic skin prepared as described above. Based on the working principle of a single-electrode mode of the friction nano generator, when a foreign object (a contact material in the figure) is in contact with a contact electrification layer (PLGA) of an electronic skin, a complete contact-separation-complete separation-contact process exists, and due to triboelectrification and electrostatic induction effects, charge transfer can occur between an intermediate electrode layer (AgNWs) and the ground, so that alternating current output is generated. Fig. 4 shows the output performance of the electronic skin at different frequencies using 0.1mm thick Polytetrafluoroethylene (PTFE) as the contact material. Relevant tests show that the maximum 95V open-circuit voltage, 1.5 muA short-circuit current, 30nC charge transfer and 130mW m can be reached-2Power density. Pressure medicineThe sensitivity can reach 0.011kPa-1As shown in fig. 5.
FIG. 6 shows the result of the permeability test of the electronic skin under different pressures, the general permeability of denim is 10mm s-1The result shows that the air permeability of the electronic skin is far higher than that of the jean. The reason is that the air permeability is enhanced by the multilayer staggered nanofiber network and a large number of three-dimensional micro-nano hierarchical holes in the structure.
Fig. 7 shows the results of the electronic skin antibacterial performance test. Staphylococcus aureus is selected as a gram-positive representative bacterium, Escherichia coli is selected as a gram-negative representative bacterium to perform an antibacterial test, and the antibacterial efficiency is calculated by comparing the number of the bacteria before and after the co-culture of the added electronic skin by a colony counting method. The related experiment results show that the silver nanowires have obvious antibacterial property on staphylococcus aureus and escherichia coli, and the antibacterial efficiency is 87% and 54% respectively. It is noted that the antibacterial efficiency can be improved by increasing the concentration of the silver nanowires, and meanwhile, the silver nanowires have broad-spectrum antibacterial property and have better antibacterial property on various bacteria, fungi and viruses, so that the antibacterial application range of the electronic skin is widened.
Fig. 8 shows the degradation of different nanofiber membranes in PBS solution for a certain period of time, in which PVA is substantially completely degraded after 3 days, PLGA begins to degrade after 21 days, and different materials degrade at different rates, so that different degradation periods can be obtained by changing the types of materials and adjusting the weight ratio of different materials.
The invention also provides an application device of the full-nanofiber electronic skin, which can fix the electronic skin at a to-be-detected moving part, when the to-be-detected part moves, the electronic skin can generate an electric signal to be output, the real-time moving state of the moving part can be detected, and the application device does not need an external power supply and realizes self-driven detection. For example, the electronic skin can be fixed on a monitoring part of a human body by the aid of the band-aid to form a wearable device, joint movement electric signal characteristics of the human body such as blinking, frowning, pulse, breathing, speaking, fingers, elbows, knees, ankles and the like can be output, so that the whole body physiology and movement real-time monitoring of the human body can be rapidly realized, and the electronic skin has great prospects in the fields of personal health monitoring, patient rehabilitation, movement performance monitoring, entertainment activities such as human body movement tracking and the like. Fig. 9 shows the electronic skin used for monitoring the motion signals of different motion angles of human fingers and elbows. Correspondingly, the application device can be applied to the aspects of human body wearing, and can also be used for detecting moving parts in the fields of robots, mechanical movement and the like.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. The full nanofiber electronic skin is characterized by comprising an upper layer nanofiber membrane, a middle layer nanofiber membrane and a lower layer nanofiber membrane which are respectively a contact electrification layer, a middle electrode layer and a bottom supporting layer, wherein,
the contact electrification layer and the bottom supporting layer are all nanofiber membranes made of biodegradable materials;
the middle electrode layer is a nanofiber membrane with a sterilization function and is electrically connected with the ground or other conductors.
2. The electronic skin according to claim 1, wherein the biodegradable material comprises one or more of polyvinyl alcohol, polylactic acid-glycolic acid copolymer, polycaprolactone, polylactic acid, polyglycolic acid, polybutylene succinate, poly-beta-hydroxybutyrate, polyurethane and cellulose, which can be used for preparing polymer material of nanofiber by electrostatic spinning.
3. The electronic skin according to claim 1 or 2, wherein the material of the intermediate electrode layer is silver, gold, copper nanowires or nanowires doped with silver, gold, copper nanoparticles with a conductive function.
4. The electronic skin according to any one of claims 1 to 3, wherein the thickness of the fibrous membrane of the contact electrification layer is preferably in the range of 5-120 μm; the fiber diameter range in the fiber membrane is 580-610 nm.
5. The electronic skin according to any one of claims 1 to 4, wherein the thickness of the bottom support layer is preferably in the range of 20-40 μm, and the diameter of the fibers in the fiber membrane is in the range of 120-150 nm.
6. The electronic skin according to claim 3, wherein the diameter of the nanowire is in the range of 150-165.
7. The electronic skin according to any one of claims 1 to 4, wherein the contact electrification layer is a biodegradable material, namely polylactic acid-glycolic acid copolymer, the middle electrode layer is silver nanowires, and the bottom support layer is a biodegradable material, namely polyvinyl alcohol.
8. An application device of full nanofiber electronic skin, which is characterized by comprising the electronic skin as claimed in any one of claims 1 to 7, wherein the electronic skin is fixed on a moving part to be detected and is used for detecting the real-time moving state of the moving part.
9. The application device of claim 8 being a wearable device.
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Address after: No.8, yangyandong 1st Road, Yanqi Economic Development Zone, Huairou District, Beijing Applicant after: Beijing Institute of Nanoenergy and Nanosystems Address before: Block C, Tiangong building, 30 Xueyuan Road, Haidian District, Beijing 100083 Applicant before: Beijing Institute of Nanoenergy and Nanosystems |
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