CN112097967A - Self-energy-supply-based flexible extensible mechanical sensing system and preparation method thereof - Google Patents
Self-energy-supply-based flexible extensible mechanical sensing system and preparation method thereof Download PDFInfo
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- CN112097967A CN112097967A CN202010968253.3A CN202010968253A CN112097967A CN 112097967 A CN112097967 A CN 112097967A CN 202010968253 A CN202010968253 A CN 202010968253A CN 112097967 A CN112097967 A CN 112097967A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
- G01L1/142—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/12—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in capacitance, i.e. electric circuits therefor
Abstract
The invention provides a self-energy-supply-based flexible extensible mechanical sensing system and a preparation method thereof, wherein the self-energy-supply-based flexible extensible mechanical sensing system comprises the following steps: the stretchable nano-generator based on the folded electrode material, the stretchable interdigital electrode super-capacitor array and the mechanical sensor based on the folded graphene electrode are connected. The nano generator is used for charging the interdigital electrode super capacitor array, and on the basis, the interdigital electrode super capacitor array is used for supplying energy to the mechanical sensor based on graphene. In the system, the nano generator based on the corrugated electrode, the supercapacitor array based on the interdigital electrode and the mechanical sensor based on the graphene with the corrugated morphology all have flexible and extensible characteristics, so that the self-powered mechanical sensor system can be applied to portable, wearable and implantable electronic device platforms.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a self-energy-supply-based flexible extensible mechanical sensing system and a preparation method thereof.
Background
In recent decades, with the wide application of intelligent flexible wearable devices in the fields of medical health monitoring, man-machine fusion, artificial intelligence and the like, flexible electronic technologies are rapidly developing towards intellectualization, integration and multi-functionalization. Although the flexible electronic device has made an important progress in reducing power consumption, the supply and consumption of energy still are the most critical limiting factors for the development of flexible electronics, and research and development of autonomous power supply flexible sensors based on novel energy efficient collection become an important research direction of flexible intelligent electronics.
In addition, the human body continuously generates a wide range of biological signals, physiological mechanical signals (e.g., tactile sensations of pressure, stress) and biochemical signals. However, the conventional mechanical sensor is too bulky and inflexible, and is difficult to meet the requirements of skin fitting, and being wearable and implantable; and an external power supply is required to provide energy, so that the service life of the sensor is shortened and environmental pollution is caused. Therefore, the friction nano generator is constructed by utilizing the physiological mechanical signals of the human body to collect energy, the energy is stored by virtue of the flexible super capacitor, the energy supply of the flexible wearable mechanical sensor is realized, and the mechanical sensing system for obtaining the self-energy supply has great scientific significance and market value.
Disclosure of Invention
Aiming at the defects and the defects of the existing sensing technology, the invention aims to provide a flexible extensible mechanical sensing system based on self-energy supply and a preparation method thereof. The interdigital electrode super capacitor array is charged by using the nanometer generator, and on the basis, the mechanical sensor based on the folded graphene is supplied with energy by means of the interdigital electrode super capacitor array. In the system, the nano generator based on the corrugated electrode, the supercapacitor array based on the interdigital electrode and the mechanical sensor based on the corrugated graphene all have flexible and extensible characteristics, so that the self-powered mechanical sensor system can be applied to portable, wearable and implantable electronic device platforms. The invention has the advantages of strong universality, easy popularization, low manufacturing cost, simple operation and the like. The wearable electronic device can effectively solve the problem that the traditional mechanical sensor is difficult to meet the requirements of skin attachment and wearability, avoids the problems of sensor service life reduction and battery pollution caused by an external power supply, promotes the application and development of wearable electronic equipment, and has wide application prospects in the fields of electronic skin, wearable physiological monitoring and treatment devices, transparent thin film flexible gate circuits and the like.
The invention not only can realize the self-energy supply of the mechanical sensor, but also can realize the flexible and extensible property of the energy supply device, the energy storage device and the sensing device, thereby realizing the purpose that the self-energy mechanical sensing system is easy to be attached to the skin and can be worn.
The invention specifically adopts the following technical scheme:
the flexible extensible mechanical sensing system based on self-powered energy is characterized by comprising a stretchable nano generator based on a folded electrode material, a stretchable interdigital electrode super capacitor array and a mechanical sensor based on a folded morphology graphene electrode, wherein the stretchable nano generator, the stretchable interdigital electrode super capacitor array and the mechanical sensor are connected;
the stretchable nanogenerator based on a pleated electrode material comprises: a plane electrode silicone resin film as an upper friction layer and a wrinkled electrode silicone resin film as a lower friction layer; the upper friction layer and the lower friction layer are connected through an elastic connecting piece arranged on the edge;
the stretchable interdigitated electrode supercapacitor array comprises: the laser-induced graphene foam supercapacitor array comprises a flexible substrate of a silicone film and a laser-induced graphene foam supercapacitor array of an interdigital structure fixed on the flexible substrate of the silicone film;
the mechanical sensor based on the corrugated morphology graphene electrode comprises: the graphene electrode comprises a folded graphene layer and a noble metal electrode on the surface of the folded graphene.
Preferably, the planar electrode silicone film comprises a planar silicone film layer and a planar electrode layer grown on the planar silicone film layer; the wrinkled electrode silicone film is obtained by releasing pre-stretching after an electrode layer grows on the pre-stretched silicone film.
Preferably, the laser-induced graphene foam supercapacitor array with the interdigital structure is provided with a solid electrolyte.
Preferably, the stretchable interdigital electrode supercapacitor array is encapsulated by a silicone film encapsulation layer.
Preferably, polydimethylsiloxane and copolyester are adopted as the silicone material; the electrode material is one or more of gold, silver, aluminum, platinum, copper, nickel, iron, zinc and magnesium; the solid electrolyte is PVA/KCl, PVA/KOH or PVA/H2SO4、PVA/H3PO4One or more of PVA/LiCl and PVA/LiOH.
Preferably, a rectifier is arranged on a connecting loop between the stretchable nano-generator based on the folded electrode material and the stretchable interdigital electrode supercapacitor array; and a current meter and a voltage meter are arranged on a connecting loop of the stretchable interdigital electrode supercapacitor array and the mechanical sensor based on the graphene electrode with the corrugated morphology.
And a method for preparing the mechanical sensing system according to the above, characterized in that: the preparation method of the stretchable nano-generator based on the folded electrode material comprises the following steps:
step A1: preparing a silicon resin film in a culture dish by using a spin coating technology;
step A2: growing a layer of electrode material on the surface of the silicon resin film by using a material growth technology to obtain a planar electrode silicon resin film;
step A3: obtaining a pre-stretched silicon resin film by using a clamp, and growing a layer of electrode material on the surface of the pre-stretched silicon resin film by using a material growth technology;
step A4: gradually releasing the prestretched silicone resin film with the electrode material on the surface to obtain a wrinkled electrode silicone resin film;
step A5: and connecting the plane electrode silicone film with the folded electrode silicone film through an elastic connecting piece, wherein the plane electrode silicone film is used as an upper friction layer, and the folded electrode silicone film is used as a lower friction layer, so that the stretchable nano-generator based on the folded electrode material is formed.
Preferably, the preparation method of the stretchable interdigital electrode supercapacitor array comprises the following steps:
step B1: adhering a polyimide film on the silicon resin film, and reducing the polyimide film by using a carbon dioxide laser to form a laser-induced graphene foam supercapacitor array with an interdigital structure;
step B2: depositing a solid electrolyte on the array of interdigitated structured laser-induced graphene foam supercapacitors;
step B3: and preparing a silicon resin film packaging layer on the surface of the laser-induced graphene foam supercapacitor array with the interdigital structure by virtue of a spin coating technology, so as to realize packaging of the supercapacitor array.
Preferably, the preparation method of the mechanical sensor based on the corrugated morphology graphene electrode comprises the following steps:
step C1: preparing 1-5 layers of graphene on a metal foil substrate by adopting a chemical vapor deposition method; then spin-coating a layer of silicone resin film on the surface of graphene, and immersing 1 mol/L FeCl at 60 DEG C3The solution was left for 8 hours to completely etch away the metal foil substrate;
step C2: cleaning a graphene volume layer on a silicon resin film, transferring the graphene volume layer onto a prestretched adhesive tape, gradually releasing stress on the adhesive tape to obtain graphene with a wrinkle appearance, and preparing a noble metal electrode on the graphene with the wrinkle appearance by using noble metal slurry.
Preferably, the material growth technology adopts electron beam evaporation or magnetron sputtering; the pre-stretching adopts single-axis stretching or multi-axis stretching; the pre-stretching degree of the silicone resin film is any value of 0-500%; capacitors in the stretchable interdigital electrode super capacitor array are connected in series or in parallel.
Compared with the prior art, the invention and the preferred scheme thereof have the advantages of strong universality, easy popularization, low manufacturing cost, simple operation and the like. The wearable electronic device can effectively solve the problem that the traditional mechanical sensor is difficult to meet the requirements of skin attachment and wearability, avoids the problems of sensor service life reduction and battery pollution caused by an external power supply, promotes the application and development of wearable electronic equipment, and has wide application prospects in the fields of electronic skin, wearable physiological monitoring and treatment devices, flexible conductive fabrics, thin film transistors, transparent thin film flexible gate circuits and the like.
Drawings
The invention is described in further detail below with reference to the following figures and detailed description:
FIG. 1 is a schematic diagram of the preparation of a silicone film flexible substrate according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an embodiment of the present invention for growing electrode material on a flexible substrate of silicone film;
FIG. 3 is a schematic diagram of an embodiment of the present invention for growing an electrode material film on a pre-stretched flexible substrate of a silicone film and obtaining a wrinkled electrode material by gradually releasing stress;
FIG. 4 is a schematic diagram of an embodiment of the present invention for mounting an elastic connection element on the surface of a corrugated electrode;
FIG. 5 is a schematic illustration of an embodiment of the present invention connecting a flat electrode material and a corrugated electrode material by a resilient connecting member;
FIG. 6 is a schematic diagram of a laser-induced graphene foam supercapacitor array with interdigitated structures prepared according to an embodiment of the present invention;
FIG. 7 is a schematic illustration of the titration of solid electrolyte on an array of interdigitated electrodes in accordance with an embodiment of the present invention;
FIG. 8 is a schematic diagram of an embodiment of the present invention for fabricating a few layers (1-5) of graphene on a metal foil substrate 8 by chemical vapor deposition;
FIG. 9 is a schematic diagram illustrating spin coating a silicone film on the surface of the grown graphene according to an embodiment of the present invention;
FIG. 10 illustrates the utilization of FeCl in an embodiment of the present invention3Etching the metal foil substrate with the solution, and obtaining a few layers of graphene schematic diagrams on the surface of the flexible extensible silicone resin film;
FIG. 11 is a schematic representation of the transfer of few layers of graphene to a pre-drawn tape according to an embodiment of the present invention;
FIG. 12 is a schematic diagram of an embodiment of the present invention gradually releasing a pre-stretched tape to obtain a wrinkled graphene;
fig. 13 is a schematic diagram of an electrode prepared on the surface of a folded graphene by using a noble metal slurry according to an embodiment of the present invention;
FIG. 14 is a schematic connection diagram of a nanogenerator based on a corrugated electrode material, an interdigital electrode array supercapacitor based on the same and a mechanical sensor based on graphene with corrugated morphology according to an embodiment of the invention;
FIG. 15 is a schematic diagram of a performance test of an embodiment of the present invention.
Detailed Description
In order to make the features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail as follows:
this example illustrates the protocol in detail by a self-powered flexible-malleable mechanical sensing system based preparation process:
fig. 1 is a process for preparing a flexible substrate of a silicone film. And (3) preparing the silicon resin film on a clean culture dish by using a spin coating method, and heating and curing to obtain the flexible and extensible silicon resin film 1. The silicone film 1 may be Polydimethylsiloxane (PDMS) and copolyester (Ecoflex).
Fig. 2 is a preparation process for growing an electrode material on a flexible substrate of a silicone film. The electrode material film 2 is grown on the silicone resin film flexible substrate using a material growth technique (magnetron sputtering, electron beam evaporation, etc.). The electrode material can be gold, silver, aluminum, platinum, copper, nickel, iron, zinc, magnesium and other conductive materials.
Fig. 3 shows the preparation process of growing an electrode material film 2 on a pre-stretched flexible substrate of a silicone resin film, and then gradually releasing the stress to obtain a wrinkled electrode material 3. The stretching mode of the pre-drawn silicone film may be uniaxial stretching and multiaxial stretching. The pre-lift of the silicone film may be any value from 0 to 500%.
Fig. 4 shows a preparation process for mounting the elastic connecting piece 4 on the surface of the corrugated electrode 3.
Fig. 5 is a manufacturing process for connecting a flat electrode material 5 and a wrinkled electrode material 3 by an elastic connection member 4, wherein a silicone resin 1 based on a flat electrode material film is used as an upper friction layer, and a wrinkled electrode material film 3 is used as a lower friction layer.
Fig. 6 is a preparation process of attaching a PI (polyimide film) film on the prepared silicone resin film 1 and reducing the PI film by using a carbon dioxide laser to prepare a graphene foam (LIG) supercapacitor array 6 with an interdigital structure.
Fig. 7 is a preparation process for titrating a solid electrolyte 7 on an interdigitated electrode array. Then, a silicon resin film packaging layer is prepared on the surface of the interdigital electrode array by means of a spin coating technology, so that the packaging of the super capacitor array is realized; the solid electrolyte can be PVA/KCl, PVA/KOH, PVA/H2SO4、PVA/H3PO4One or more of PVA/LiCl and PVA/LiOH. The interdigital electrode super capacitor array can realize series connection and parallel connection, and the regulation and control of output voltage and current are realized.
FIG. 8 shows a process for preparing a few layers (1-5) of graphene 9 on a metal foil substrate 8 by chemical vapor deposition: the metal foil substrate may be copper, nickel, or the like.
Fig. 9 is a preparation process of spin-coating a silicon resin film on the surface of the grown graphene 9.
FIG. 10 is a schematic representation of the utilization of FeCl3And etching the metal foil substrate by the solution, and obtaining a preparation process of a few layers of graphene 9 on the surface of the flexible extensible silicone resin film. The process of fig. 8-10 is: preparing a few layers (1-5) of graphene 9 on a clean metal foil substrate 8 by adopting a chemical vapor deposition method, then spin-coating a layer of silicon resin film 1 on the surface of the graphene, and immersing the graphene into 1 mol/L FeCl at 60 DEG C3The solution was left for 8 hours to completely etch away the metal foil substrate.
Fig. 11 is a preparation process for transferring a few layers of graphene 9 onto a pre-lifted tape 10.
Fig. 12 is a preparation process for gradually releasing the pre-drawn tape 10 to obtain the wrinkled graphene 11.
Fig. 13 is a preparation process of preparing the noble metal electrode 12 on the surface of the wrinkled graphene by using the noble metal slurry. The noble metal paste may be gold, silver, platinum, or the like.
Fig. 14 and fig. 15 are schematic diagrams of a self-powered flexible extensible mechanical sensing system constructed by connection of a nanogenerator based on a corrugated electrode material, an interdigital electrode array super capacitor based on a mechanical sensor based on a corrugated morphology graphene, wherein the lead used for connection can be a metal (platinum, gold, silver, copper and the like) lead or a conductive adhesive tape and the like. The nano-generator based on the corrugated electrode material can convert mechanical energy such as vibration, stretching, distortion and the like into electric energy. The output signals of the nanometer generator under different frequency conditions, the charging curve graph of the super capacitor under the condition of utilizing the nanometer generator to supply energy, and the mechanical sensing performance of the mechanical sensor under the condition of supplying energy by the super capacitor array can be any value from 0 to 220 percent. The self-powered mechanical sensor has the characteristics of high sensitivity and wide measurement range. ,
the present invention is not limited to the above preferred embodiments, and other various forms of flexible and extensible mechanical sensing systems based on self-energizing and methods of making can be derived by anyone in light of the present disclosure, and all equivalent changes and modifications that can be made in accordance with the present invention shall fall within the scope of the present invention.
Claims (10)
1. A self-powered flexible-malleable mechanical sensing system, comprising: the stretchable nano generator based on the folded electrode material, the stretchable interdigital electrode super capacitor array and the mechanical sensor based on the folded graphene electrode are connected;
the stretchable nanogenerator based on a pleated electrode material comprises: a plane electrode silicone resin film as an upper friction layer and a wrinkled electrode silicone resin film as a lower friction layer; the upper friction layer and the lower friction layer are connected through an elastic connecting piece arranged on the edge;
the stretchable interdigitated electrode supercapacitor array comprises: the laser-induced graphene foam supercapacitor array comprises a flexible substrate of a silicone film and a laser-induced graphene foam supercapacitor array of an interdigital structure fixed on the flexible substrate of the silicone film;
the mechanical sensor based on the corrugated morphology graphene electrode comprises: the graphene electrode comprises a folded graphene layer and a noble metal electrode on the surface of the folded graphene.
2. The self-powered flexible malleable mechanical sensing system according to claim 1, wherein: the planar electrode silicon resin film comprises a planar silicon resin film layer and a planar electrode layer growing on the planar silicon resin film layer; the wrinkled electrode silicone film is obtained by releasing pre-stretching after an electrode layer grows on the pre-stretched silicone film.
3. The self-powered flexible malleable mechanical sensing system according to claim 1, wherein: and the laser-induced graphene foam supercapacitor array with the interdigital structure is provided with solid electrolyte.
4. The self-powered flexible malleable mechanical sensing system according to claim 1, wherein: the stretchable interdigital electrode super capacitor array is packaged through a silicon resin film packaging layer.
5. A self-powered flexible malleable mechanical sensing system, according to claim 3, characterised in that: the silicone resin material adopts polydimethylsiloxane and copolyester; the electrode material is one or more of gold, silver, aluminum, platinum, copper, nickel, iron, zinc and magnesium; the solid electrolyte is PVA/KCl, PVA/KOH or PVA/H2SO4、PVA/H3PO4One or more of PVA/LiCl and PVA/LiOH.
6. The self-powered flexible malleable mechanical sensing system according to claim 1, wherein: a rectifier is arranged on a connecting loop between the stretchable nano-generator based on the folded electrode material and the stretchable interdigital electrode super capacitor array; and a current meter and a voltage meter are arranged on a connecting loop of the stretchable interdigital electrode supercapacitor array and the mechanical sensor based on the graphene electrode with the corrugated morphology.
7. The method for preparing a self-powered flexible-malleable mechanical sensing system, according to claim 1, characterized in that: the preparation method of the stretchable nano-generator based on the folded electrode material comprises the following steps:
step A1: preparing a silicon resin film in a culture dish by using a spin coating technology;
step A2: growing a layer of electrode material on the surface of the silicon resin film by using a material growth technology to obtain a planar electrode silicon resin film;
step A3: obtaining a pre-stretched silicon resin film by using a clamp, and growing a layer of electrode material on the surface of the pre-stretched silicon resin film by using a material growth technology;
step A4: gradually releasing the prestretched silicone resin film with the electrode material on the surface to obtain a wrinkled electrode silicone resin film;
step A5: and connecting the plane electrode silicone film with the folded electrode silicone film through an elastic connecting piece, wherein the plane electrode silicone film is used as an upper friction layer, and the folded electrode silicone film is used as a lower friction layer, so that the stretchable nano-generator based on the folded electrode material is formed.
8. The method for preparing a self-powered flexible-malleable mechanical sensing system, according to claim 7, characterized in that: the preparation method of the stretchable interdigital electrode supercapacitor array comprises the following steps:
step B1: adhering a polyimide film on the silicon resin film, and reducing the polyimide film by using a carbon dioxide laser to form a laser-induced graphene foam supercapacitor array with an interdigital structure;
step B2: depositing a solid electrolyte on the array of interdigitated structured laser-induced graphene foam supercapacitors;
step B3: and preparing a silicon resin film packaging layer on the surface of the laser-induced graphene foam supercapacitor array with the interdigital structure by virtue of a spin coating technology, so as to realize packaging of the supercapacitor array.
9. The method for preparing a self-powered flexible-malleable mechanical sensing system, according to claim 8, characterized in that: the preparation method of the mechanical sensor based on the corrugated morphology graphene electrode comprises the following steps:
step C1: preparing 1-5 layers of graphene on a metal foil substrate by adopting a chemical vapor deposition method; then spin-coating a layer of silicone resin film on the surface of graphene, and immersing 1 mol/L FeCl at 60 DEG C3The solution was left for 8 hours to completely etch away the metal foil substrate;
step C2: cleaning a graphene volume layer on a silicon resin film, transferring the graphene volume layer onto a prestretched adhesive tape, gradually releasing stress on the adhesive tape to obtain graphene with a wrinkle appearance, and preparing a noble metal electrode on the graphene with the wrinkle appearance by using noble metal slurry.
10. The method for preparing a self-powered flexible-malleable mechanical sensing system, according to claim 9, characterized in that: the material growth technology adopts electron beam evaporation or magnetron sputtering; the pre-stretching adopts single-axis stretching or multi-axis stretching; the pre-stretching degree of the silicone resin film is any value of 0-500%; capacitors in the stretchable interdigital electrode super capacitor array are connected in series or in parallel.
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| CN113943439A (en) * | 2021-05-08 | 2022-01-18 | 天津科技大学 | Method for preparing GO/rGO micro-wrinkle humidity-sensitive film by biodegradable shape memory material |
| CN114777965A (en) * | 2022-04-13 | 2022-07-22 | 中北大学 | Flexible capacitive pressure sensor and preparation method thereof |
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