CN115346804A - Self-powered sensor circuit platform with embedded super capacitor and preparation method thereof - Google Patents
Self-powered sensor circuit platform with embedded super capacitor and preparation method thereof Download PDFInfo
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- CN115346804A CN115346804A CN202110522059.7A CN202110522059A CN115346804A CN 115346804 A CN115346804 A CN 115346804A CN 202110522059 A CN202110522059 A CN 202110522059A CN 115346804 A CN115346804 A CN 115346804A
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 17
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 238000003306 harvesting Methods 0.000 claims description 6
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- 239000004677 Nylon Substances 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001652 electrophoretic deposition Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000001883 metal evaporation Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000004299 exfoliation Methods 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 239000008151 electrolyte solution Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 239000010959 steel Substances 0.000 description 2
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- 238000009825 accumulation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses self-powered sensor circuit platform with embedded super capacitor and a preparation method thereof. The preparation method comprises the following steps: (1) Spraying a dispersion liquid I containing an active material on an insulating flexible substrate covered with a hollowed mask plate by adopting a centrifugal method to obtain a circuit platform Q; (2) And dropwise adding electrolyte to the electrode of the super capacitor on the circuit platform Q to form an embedded super capacitor, and obtaining the self-powered sensor circuit platform of the embedded super capacitor. The preparation method adopts a centrifugal method to prepare the embedded super capacitor with larger capacity of the self-powered sensor circuit platform with the embedded super capacitor.
Description
Technical Field
The application relates to a preparation method of a circuit platform, and belongs to the technical field of sensors.
Background
The sensor is very important in industrial production and daily life, can measure signals such as sound, light, electricity, heat, force and the like generated by the environment and human body and acquire corresponding information, and has the function of ensuring the health of people and the normal operation of industrial production. The traditional sensor has the defects of large size, heavy weight and inconvenience in carrying, and power supply equipment of the traditional sensor needs to be charged frequently, so that inconvenience is brought to practical application. For this reason, it is necessary to develop a self-powered sensor that is light in weight, small in size, good in flexibility, and free from external power supply, so as to meet the demand for the next-generation sensor.
Disclosure of Invention
According to one aspect of the application, a method for manufacturing a self-powered sensor circuit platform with an embedded super capacitor is provided, wherein the method for manufacturing the self-powered sensor circuit platform with the embedded super capacitor adopts a centrifugal method to manufacture the embedded super capacitor with a larger capacity.
A preparation method of a self-powered sensor circuit platform with an embedded super capacitor comprises the following steps:
(1) Spraying a dispersion liquid I containing an active material on an insulating flexible substrate covered with a hollowed mask plate by adopting a centrifugal method to obtain a circuit platform Q;
(2) And dropwise adding electrolyte to the electrode of the super capacitor on the circuit platform Q to form an embedded super capacitor, and obtaining the self-powered sensor circuit platform of the embedded super capacitor.
Optionally, the active material is selected from at least one of graphene, carbon nanotubes, conductive polymers, transition metal carbides, transition metal nitrides, transition metal carbonitrides.
Optionally, the graphene is selected from at least one of graphene oxide, reduced graphene oxide, electrochemically exfoliated graphene, heteroatom doped graphene;
the carbon nano tube is selected from at least one of a single-walled carbon nano tube and a multi-walled carbon nano tube;
the conductive polymer is selected from polyaniline, polypyrrole, polythiophene and polyethylene dioxythiophene: at least one of polystyrene sulfonic acid;
the transition metal carbide is selected from Ti 3 C 2 、Ti 2 C、Ti 4 C 3 、Mo 2 C、Zr 3 C 2 At least one of;
the transition metal nitride is selected from Ti 3 N 2 ；
The transition metal carbonitride is selected from Ti 3 CN。
Optionally, the insulating flexible substrate is selected from any one of polyethylene terephthalate, paper, polyimide, polydimethylsiloxane, nylon, and silk.
Optionally, the solvent of the dispersion liquid I is selected from at least one of water, ethanol, methanol, isopropanol, acetone, ethylene glycol, dimethyl sulfoxide, N-dimethylformamide, and N-methylpyrrolidone.
Optionally, the concentration of each active material in the dispersion I is 0.01-100 mg mL -1 。
Optionally, the concentration of each active material in the dispersion I is 0.01-100 mg mL -1 。
Optionally, the concentration of each active material in the dispersion I is 0.03-50 mg mL -1 。
Optionally, the concentration of each active material in the dispersion I is 0.05-20 mg mL -1 。
Optionally, the concentration of each active material in the dispersion I is 0.1-10 mg mL -1 。
Optionally, the active materials in the dispersion liquid I are graphene oxide and polyethylene dioxythiophene: polystyrene sulfonic acid, wherein the concentration of the graphene oxide is 1-8 mg mL -1 The weight ratio of the polyethylene dioxythiophene: the concentration of the polystyrene sulfonic acid is 0.3-3 mg mL -1 ；
Or graphene oxide and a multi-walled carbon nanotube, wherein the concentration of the graphene oxide is 1-10 mg/mL, and the concentration of the multi-walled carbon nanotube is 0.5-4 mg/mL;
or polyethylene dioxythiophene: polystyrene sulfonic acid, said polyethylene dioxythiophene: the concentration of the polystyrene sulfonic acid is 3-10 mg mL -1 ；
Or Ti 3 C 2 Said Ti 3 C 2 The concentration of (A) is 7-15 mg mL -1 。
Optionally, the hollowed mask plate is selected from at least one of polyethylene terephthalate, paper, polyimide, polydimethylsiloxane, nylon, silk, copper, aluminum and steel.
Optionally, the pattern of the hollowed-out mask plate is at least one selected from a line segment shape, a curve shape and a broken line shape.
Optionally, the centrifugation process conditions are: the rotating speed is 100-10000 rpm, the heating temperature is 30-200 ℃, and the centrifugation time is 5-60 min.
Optionally, the lower rotational speed limit is selected from 100, 300, 500, 800, 1000, 1500, 2000rpm; the upper limit is selected from 1000, 1500, 2000, 4000, 6000, 8000, 10000rpm.
Optionally, the lower heating temperature limit is selected from 30, 35, 40, 50, 60 ℃; the upper limit is selected from 40, 50, 60, 80, 120, 150, 200 ℃.
Optionally, the upper centrifugation time limit is selected from 15, 20, 30, 40, 50, 60min; the lower limit is selected from 10, 15, 20, 30, 40, 50min.
Optionally, the spraying process further comprises a post-treatment after the spraying process, wherein the post-treatment is at least one selected from reduction, electrochemical deposition, electrophoretic deposition and metal evaporation.
Optionally, the electrolyte contains at least one of an acid, a base, or a salt.
Optionally, the acid is selected from sulfuric acid and/or phosphoric acid; the alkali is selected from potassium hydroxide; the salt is selected from sodium sulfate, lithium chloride, 1-ethyl-3-methylimidazolium tetrafluoroborate and lithium bistrifluoromethanesulfonylimide.
Alternatively, the electrolyte is selected from any one of a sulfuric acid solution, a phosphoric acid solution, a potassium hydroxide solution, a sodium sulfate solution, a lithium chloride solution, a mixture of sulfuric acid and polyvinyl alcohol, a mixture of phosphoric acid and polyvinyl alcohol, a mixture of potassium hydroxide and polyvinyl alcohol, a mixture of lithium chloride and polyvinyl alcohol, a mixture of sodium sulfate and polyvinyl alcohol, a mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and polyvinylidene fluoride, and a mixture of lithium bistrifluoromethanesulfonimide and polyvinylidene fluoride.
Optionally, the addition amount of the electrolyte is 0.5-2 g/cm 2 。
According to another aspect of the present application, there is provided a self-powered sensor circuit platform with embedded super capacitor, comprising: circuit platform Q and embedded ultracapacitor system in circuit platform Q.
Optionally, the circuit platform Q comprises a circuit I and a circuit II;
the circuit I and the circuit II are not in contact with each other;
the circuit I is provided with a main circuit A;
the circuit II is provided with a main circuit M;
the branch circuit of the main circuit a and the branch circuit of the main circuit M appear in pairs;
the main circuit A has a branch circuit B 1 ～B x (ii) a And
branch circuit C 1 (ii) a And
branch circuit D 1 ；
The main circuit M has a branch circuit N 1 ～N x Said branch circuit N 1 ～N x And the branch circuit B 1 ～B x As a supercapacitor electrode; and
branch circuit O 1 Said branch circuit O 1 And the branch circuit C 1 For accessing the energy harvesting device 1; and
branch circuit P 1 Said branch circuit P 1 And the branch circuit D 1 For accessing the sensor 1;
and x is a natural number.
Optionally, the main circuit a further has a branch circuit C 2 ～C y ，
The main circuit M also has a branch circuit O 2 ～O y Said branch circuit O 2 ～O y And the branch circuit C 2 ～C y Used for accessing the energy collecting devices 2-y;
and y is an integer greater than 2.
Optionally, the main circuit a further has a branch circuit D 2 ～D z ，
The main circuit M also has a branch circuit P 2 ～P z Said branch circuit P 2 ～P z And the branch circuit D 2 ～D z Used for accessing energy sensors 2-z;
and z is an integer greater than 2.
Optionally, the shape of the main circuit and branch circuit of the circuit I and the main circuit and branch circuit of the circuit II is selected from at least one of a segment shape, a curved shape and a dogleg shape.
According to another aspect of the application, a self-powered sensor is provided, wherein the self-powered sensor comprises the self-powered sensor circuit platform with the embedded super capacitor prepared by the preparation method described in any one of the above or the self-powered sensor circuit platform with the embedded super capacitor, an energy collecting device and a sensor, and the energy collecting device and the sensor are connected into the self-powered sensor circuit platform with the embedded super capacitor.
Optionally, the energy harvesting device is selected from at least one of a solar cell, a triboelectric nanogenerator, a piezoelectric nanogenerator;
the sensor is selected from at least one of a mechanical sensor, a temperature sensor, a gas sensor, a humidity sensor and an optical sensor.
The beneficial effects that this application can produce include:
(1) According to the preparation method of the self-powered sensor circuit platform with the embedded super capacitor, the dispersion liquid containing the active materials is sprayed on the insulating flexible substrate by a centrifugal method, the preparation method is simple, the efficiency is high, the active materials are more densely accumulated on the substrate, and the embedded super capacitor prepared by the method has larger capacity.
(2) The application provides a preparation method of self-powered sensor circuit platform of embedded ultracapacitor system, through the centrifugal rotational speed of control, combines concentration, the heating temperature of dispersion simultaneously, can further improve embedded ultracapacitor system's capacity.
Drawings
Fig. 1 is a schematic diagram of a circuit platform of a self-powered sensor with embedded super capacitor prepared in embodiments 1 to 3 and comparative example 1 of the present application.
Fig. 2 is a schematic diagram of a self-powered sensor circuit platform with embedded super capacitor prepared according to embodiment 4 of the present application.
Fig. 3 is a scanning electron microscope photograph of a thin film of a mixture of reduced graphene oxide and multi-walled carbon nanotubes in a self-powered sensor prepared in example 2 of the present application.
Fig. 4 shows electrochemical exfoliation of graphene and polyethylenedioxythiophene in a self-powered sensor prepared in comparative example 1 of the present application: scanning electron micrographs of polystyrene sulfonic acid blend films.
In fig. 1 and 2, Q represents a circuit platform to which the supercapacitor electrolyte is not added, and comprises a circuit I and a circuit II which are not in contact with each other; the circuit I is provided with a main circuit A; the circuit II is provided with a main circuit M; the branch circuit of the main circuit a and the branch circuit of the main circuit M appear in pairs. The main circuit A has a branch circuit B 1 ～B 4 (ii) a And branch circuit C 1 (ii) a And a branch circuit D 1 . The main circuit M has a branch circuit N 1 ～N 4 Said branch circuit N 1 ～N 4 And the branch circuit B 1 ～B 4 As a supercapacitor electrode; and a branch circuit O 1 Said branch circuit O 1 And the branch circuit C 1 For accessing the energy harvesting device 1; and a branch circuit P 1 Said branch circuit P 1 And the branch circuit D 1 For accessing the sensor 1. Wherein, the main circuit A in FIG. 2 also has a branch circuit D 2 The main circuit M also has a branch circuit P 2 Said branch circuit P 2 And the branch circuit D 2 For accessing the energy sensor 2. Supercapacitor electrode subcircuit N in fig. 1 and 2 1 ～N 4 And branch circuit B 1 ～B 4 Dropping electrolyte to form embedded super capacitor, obtaining self-powered sensor circuit platform of embedded super capacitor, and adding electrolyte into branch circuit O 1 And branch circuit C 1 Connected to an energy-collecting device 1 in a branch circuit P 1 、P 2 And a branch circuit D 1 、D 2 For accessing the energy sensors 1, 2, self-energizing sensors are available.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Other materials used in the present application may be commercially available unless otherwise specified.
Among them, polyethylene dioxythiophene used in the present application: polystyrene sulfonic acid was purchased from Heley, germany.
As a specific embodiment, the present application provides a method for preparing a self-powered sensor circuit platform with an embedded supercapacitor, which specifically includes the following steps:
(1) An insulated flexible substrate is placed in a roller of a centrifugal spraying instrument, and a hollow mask plate with patterns is covered on the substrate.
(2) The drum of the centrifugal spray apparatus was rotated and heated to continuously spray the dispersion containing the active material onto the drum.
(3) And after spraying, taking down the mask plate, carrying out post-treatment on the patterned active material obtained on the insulating substrate, and dropwise adding electrolyte at the electrode position of the super capacitor to obtain the self-powered sensor circuit platform embedded with the super capacitor.
And then the energy collecting device and the sensor are connected to corresponding positions in a self-powered sensor circuit platform of the embedded super capacitor, so that the self-powered sensor is formed.
Optionally, the flexible substrate in step (1) includes polyethylene terephthalate, paper, polyimide, polydimethylsiloxane, nylon, silk.
Optionally, the hollow-out pattern of the mask plate in the step (1) is the obtained pattern of the self-powered sensor circuit platform embedded with the super capacitor;
the super capacitor electrode pattern comprises one or more of cross fingers, line segment shapes, curved shapes, concentric circles and zigzag shapes;
the integrated circuit pattern comprises one or more of a line segment shape, a curve shape and a fold line shape.
Optionally, the mask plate in step (1) is made of polyethylene terephthalate, paper, polyimide, polydimethylsiloxane, nylon, silk, copper, aluminum, or steel.
Optionally, the rotation speed of the centrifugal spraying instrument in the step (2) is 100-10000 rpm, and the heating temperature is 30-200 ℃.
Optionally, the active material in step (2) is one or more of graphene, carbon nanotubes, conductive polymer, and transition metal carbon/nitrogen/carbon nitride.
Optionally, the graphene is one or more of graphene oxide, reduced graphene oxide, electrochemically exfoliated graphene, and heteroatom doped graphene;
the carbon nano tube is one or the combination of two of a single-walled carbon nano tube and a multi-walled carbon nano tube;
the conductive polymer is polyaniline, polypyrrole, polythiophene and polyethylene dioxythiophene: one or more of polystyrene sulfonic acid;
the transition metal carbon/nitrogen/carbon nitride is Ti 3 C 2 、Ti 3 N 2 、Ti 3 C 2 、Ti 3 CN、Ti 2 C、Ti 4 C 3 、Mo 2 C、Zr 3 C 2 、Ti 3 C 2 One or a combination of more than one of them.
Optionally, the solvent of the dispersion in step (2) is one or more of water, ethanol, methanol, isopropanol, acetone, ethylene glycol, dimethyl sulfoxide, N-dimethylformamide, and N-methylpyrrolidone.
Optionally, the concentration of the graphene dispersion liquid in the step (2) is 0.01-100 mg mL -1 ；
The concentration of the carbon nano tube dispersion liquid is 0.01-100 mg mL -1 ；
The concentration of the conductive polymer dispersion liquid is 0.01-100 mg mL -1 ；
The concentration of the dispersion of the transition metal carbide, the transition metal nitride and the transition metal carbonitride is 0.01 to 100mg mL -1 ；
When the active material is a combination of more than one material, the respective concentrations are the same as described above.
Optionally, the post-treatment of the patterned active material in step (3) includes reduction, electrochemical deposition, electrophoretic deposition, metal evaporation, and other treatment methods, and also includes no treatment.
Optionally, the electrolyte in step (3) is one of a sulfuric acid solution, a phosphoric acid solution, a potassium hydroxide solution, a sodium sulfate solution, a lithium chloride solution, sulfuric acid/polyvinyl alcohol, phosphoric acid/polyvinyl alcohol, potassium hydroxide/polyvinyl alcohol, lithium chloride/polyvinyl alcohol, sodium sulfate/polyvinyl alcohol, 1-ethyl-3-methylimidazolium tetrafluoroborate/polyvinylidene fluoride, lithium bistrifluoromethanesulfonylimide/polyvinylidene fluoride, and the like.
Optionally, the energy harvesting device comprises at least one of a solar cell, a triboelectric nanogenerator, a piezoelectric nanogenerator; the sensor comprises at least one of a mechanical sensor, a temperature sensor, a gas sensor, a humidity sensor and an optical sensor.
Example 1
Preparation of self-powered sensor circuit platform with embedded super capacitor
Polyethylene terephthalate as a substrate and polyethylene terephthalate having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 1 were used as a mask plate. Placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument, wherein the rotating speed of the roller of the centrifugal spraying instrument is 1500rpm, the heating temperature is 60 ℃, and the sprayed dispersion liquid is 3mg/mL of graphene oxide and 1mg/mL of polyethylene dioxythiophene: spraying the polystyrene sulfonic acid mixed aqueous dispersion for 10min. After the spraying is finished, the obtained graphene oxide and polyethylene dioxythiophene: the pattern of the polystyrenesulfonic acid mixture was reduced with hydroiodic acid to give a self-powered sensor circuit platform Q as shown in FIG. 1, and 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And a branch circuit B 1 ～B 4 ) And a self-powered sensor circuit platform with the embedded super capacitor can be obtained.
Then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 Connecting sensor 1 with ammonia gas sensorGo into branch circuit P 1 And a branch circuit D 1 And obtaining the self-powered sensor.
The capacity of the embedded super capacitor in the self-powered sensor obtained by testing is 32F/cm 3 。
Example 2
Preparation of self-powered sensor circuit platform with embedded super capacitor
Polyethylene terephthalate as a substrate and polyethylene terephthalate having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 1 were used as a mask plate. And (3) placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument, wherein the rotating speed of the roller of the centrifugal spraying instrument is 1000rpm, the heating temperature is 50 ℃, the sprayed dispersion liquid is 3mg/mL of graphene oxide and 1mg/mL of multi-walled carbon nano tube aqueous dispersion liquid, and the spraying time is 15min. After the spraying is finished, reducing the obtained pattern of the mixture of the graphene oxide and the multi-walled carbon nano tube by using hydroiodic acid to obtain a self-powered sensor circuit platform Q shown in figure 1, and mixing 1g/cm 2 A phosphoric acid and polyvinyl alcohol mixture (1 1 ～N 4 And branch circuit B 1 ～B 4 ) And the self-powered sensor circuit platform with the embedded super capacitor can be obtained. Wherein, the scanning electron microscope picture of the reduced graphene oxide and multi-walled carbon nanotube mixed material film is shown in figure 3, and the dense accumulation of the electrode material can be seen.
Then the energy collecting device 1 friction nanometer generator is connected into a branch circuit O 1 And branch circuit C 1 Connecting the pressure sensor of sensor 1 to the branch circuit P 1 And a branch circuit D 1 And obtaining the self-powered sensor.
Example 3
Polyimide was used as a substrate, and an aluminum foil having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 1 was used as a mask plate. Placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument at a rotation speed of 1000rpm and a heating temperature of 50 deg.C, wherein the sprayed dispersion is 5mg/mConductive polymer of L polyethylene dioxythiophene: spraying the aqueous dispersion of polystyrene sulfonic acid for 10min. After the spraying is finished, the spraying is carried out without post-treatment, and then the spraying amount is 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And branch circuit B 1 ～B 4 ) And obtaining the self-powered sensor circuit platform Q shown in figure 1.
Then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 Connecting the carbon monoxide sensor of sensor 1 to the branch circuit P 1 And a branch circuit D 1 And obtaining the self-powered sensor.
Example 4
Polyimide was used as a substrate, and an aluminum foil having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 2 was used as a mask plate. Placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument, wherein the roller of the centrifugal spraying instrument rotates at 2000rpm, the heating temperature is 40 ℃, and the sprayed dispersion liquid is 10mg/mL of transition metal carbide Ti 3 C 2 The spraying time of the aqueous dispersion of (1) was 20min. After the spraying is finished, the spraying is carried out without post-treatment, and then the spraying amount is 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And a branch circuit B 1 ～B 4 ) Namely, the self-powered sensor circuit platform Q shown in figure 2 is obtained,
then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 The temperature sensor of the sensor 1 is connected to the branch circuit P 1 And a branch circuit D 1 The sensor 2 is connected to the branch circuit P 2 And a branch circuit D 2 And obtaining the self-powered sensor.
The circuit platform has two sensor positions and generality, which indicates that the circuit platform can be customized for any number of sensor access points by using the method, and then the energy collecting device and the two sensors are accessed to corresponding positions in the circuit to obtain the self-powered sensor.
Example 5
Preparation of self-powered sensor circuit platform with embedded super capacitor
Polyethylene terephthalate as a substrate and polyethylene terephthalate having a hollow pattern in the shape of a self-powered sensor circuit stage as shown in fig. 1 as a mask plate were used. Placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument, wherein the rotating speed of the roller of the centrifugal spraying instrument is 500rpm, the heating temperature is 60 ℃, and the sprayed dispersion liquid is 3mg/mL of graphene oxide and 1mg/mL of polyethylene dioxythiophene: spraying the aqueous dispersion of polystyrene sulfonic acid mixture for 10min. After the spraying is finished, the obtained graphene oxide and polyethylene dioxythiophene: the pattern of the polystyrene sulfonic acid mixture was reduced with hydroiodic acid to give the self-powered sensor circuit platform Q shown in FIG. 1, and then 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And branch circuit B 1 ～B 4 ) And the self-powered sensor circuit platform with the embedded super capacitor can be obtained.
Then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 Connecting the ammonia sensor of sensor 1 into the branch circuit P 1 And a branch circuit D 1 And obtaining the self-powered sensor.
The capacity of the embedded super capacitor in the self-powered sensor obtained by the test is 28F/cm 3 。
Example 6
Preparation of self-powered sensor circuit platform with embedded super capacitor
Polyethylene terephthalate as a substrate and polyethylene terephthalate having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 1 were used as a mask plate. Placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument at 1500rpm, heating temperature of 45 deg.C, and spraying dispersion of 3mgGraphene oxide/mL and polyethylene dioxythiophene 1 mg/mL: spraying the polystyrene sulfonic acid mixed aqueous dispersion for 10min. After the spraying is finished, the obtained graphene oxide and polyethylene dioxythiophene: the pattern of the polystyrene sulfonic acid mixture was reduced with hydroiodic acid to give the self-powered sensor circuit platform Q shown in FIG. 1, and then 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And a branch circuit B 1 ～B 4 ) And a self-powered sensor circuit platform with the embedded super capacitor can be obtained.
Then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 Connecting the ammonia sensor of sensor 1 into the branch circuit P 1 And a branch circuit D 1 And obtaining the self-powered sensor.
The capacity of the embedded super capacitor in the self-powered sensor obtained by testing is 34F/cm 3 。
Example 7
Preparation of self-powered sensor circuit platform with embedded super capacitor
Polyethylene terephthalate as a substrate and polyethylene terephthalate having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 1 were used as a mask plate. Placing the substrate covered with the mask plate in a roller of a centrifugal spraying instrument, wherein the rotating speed of the roller of the centrifugal spraying instrument is 1500rpm, the heating temperature is 60 ℃, and the sprayed dispersion liquid is 1.5mg/mL of graphene oxide and 1.0mg/mL of polyethylene dioxythiophene: spraying the aqueous dispersion of polystyrene sulfonic acid mixture for 10min. After the spraying is finished, the obtained graphene oxide and polyethylene dioxythiophene: the pattern of the polystyrenesulfonic acid mixture was reduced with hydroiodic acid to give a self-powered sensor circuit platform Q as shown in FIG. 1, and 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And a branch circuit B 1 ～B 4 ) To obtain the embedded superA self-powered sensor circuit platform of a capacitor.
Then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 Connecting sensor 1 and ammonia sensor into branch circuit P 1 And a branch circuit D 1 And obtaining the self-powered sensor.
The capacity of the embedded super capacitor in the self-powered sensor obtained by the test is 35F/cm 3 。
Comparative example 1
Polyethylene terephthalate as a substrate and polyethylene terephthalate having a hollow pattern in the shape of a self-energizing sensor circuit stage as shown in fig. 1 were used as a mask plate. The heating temperature is 80 ℃, and the heating temperature is 10mg/mL of electrochemical stripping graphene and polyethylene dioxythiophene which are sprayed conventionally: an isopropyl alcohol dispersion of polystyrene sulfonic acid (1. After the spraying is finished, the spraying is carried out without post-treatment, and then the spraying amount is 1g/cm 2 A mixture of sulfuric acid and polyvinyl alcohol (1 mass ratio) was dropwise added to the supercapacitor electrode part (branch circuit N) 1 ～N 4 And branch circuit B 1 ～B 4 ) Namely, the self-powered sensor circuit platform Q shown in figure 1 is obtained,
then the solar cell of the energy collecting device 1 is connected into the branch circuit O 1 And branch circuit C 1 The temperature sensor of the sensor 1 is connected to the branch circuit P 1 And a branch circuit D 1 Connecting the humidity sensor 2 to the branch circuit P 2 And a branch circuit D 2 And obtaining the self-powered sensor.
Due to the lack of centrifugal force and shearing force in conventional spraying, the obtained graphene and polyethylene dioxythiophene: the composite material film of the polystyrene sulfonic acid is loose, and the specific capacity of the embedded super capacitor in the self-powered sensor is 14.6F/cm through testing 3 。
Example 8
Self-powered sensor circuit platform scanning electron microscope characterization with embedded super capacitor
The characterization results of the scanning electron microscope of the self-powered sensor circuit platform of the embedded supercapacitor prepared in example 2 and the self-powered sensor circuit platform of the embedded supercapacitor prepared in comparative example 1 are shown in fig. 3 and fig. 4, respectively, and it can be seen from the pictures that the active materials of the self-powered sensor circuit platform of the embedded supercapacitor prepared in example 2 are more densely packed on the substrate.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of a self-powered sensor circuit platform with an embedded super capacitor is characterized by comprising the following steps:
(1) Spraying a dispersion liquid I containing an active material on an insulating flexible substrate covered with a hollowed mask plate by adopting a centrifugal method to obtain a circuit platform Q;
(2) And dropwise adding electrolyte to the electrode of the super capacitor on the circuit platform Q to form an embedded super capacitor, and obtaining the self-powered sensor circuit platform of the embedded super capacitor.
2. The production method according to claim 1, wherein the active material is selected from at least one of graphene, carbon nanotubes, conductive polymers, transition metal carbides, transition metal nitrides, and transition metal carbonitrides;
preferably, the graphene is at least one selected from graphene oxide, reduced graphene oxide, electrochemical exfoliation graphene, and heteroatom-doped graphene;
the carbon nano tube is selected from at least one of a single-walled carbon nano tube and a multi-walled carbon nano tube;
the conductive polymer is selected from polyaniline, polypyrrole, polythiophene and polyethylene dioxythiophene: at least one of polystyrene sulfonic acid;
the transition metal carbide is selected from Ti 3 C 2 、Ti 2 C、Ti 4 C 3 、Mo 2 C、Zr 3 C 2 At least one of (a);
the transition metal nitride is selected from Ti 3 N 2 ；
The transition metal carbonitride is selected from Ti 3 CN；
Preferably, the insulating flexible substrate is selected from any one of polyethylene terephthalate, paper, polyimide, polydimethylsiloxane, nylon, and silk.
3. The production method according to claim 1, wherein the solvent of the dispersion I is at least one selected from the group consisting of water, ethanol, methanol, isopropanol, acetone, ethylene glycol, dimethyl sulfoxide, N-dimethylformamide, and N-methylpyrrolidone;
preferably, the concentration of each active material in the dispersion I is 0.01-100 mg mL -1 ；
Preferably, the active materials in the dispersion liquid I are graphene oxide and polyethylene dioxythiophene: polystyrene sulfonic acid, wherein the concentration of the graphene oxide is 1-8 mg mL -1 The polyethylene dioxythiophene: the concentration of the polystyrene sulfonic acid is 0.3-3 mg mL -1 ；
Or graphene oxide and a multi-walled carbon nanotube, wherein the concentration of the graphene oxide is 1-10 mg/mL, and the concentration of the multi-walled carbon nanotube is 0.5-4 mg/mL;
or polyethylene dioxythiophene: polystyrene sulfonic acid, said polyethylene dioxythiophene: the concentration of the polystyrene sulfonic acid is 3-10 mg mL -1 ；
Or Ti 3 C 2 Said Ti 3 C 2 The concentration of (A) is 7-15 mg mL -1 。
4. The method of claim 1, wherein the centrifugation is performed under the following conditions: the rotating speed is 100-10000 rpm, the heating temperature is 30-200 ℃, and the centrifugation time is 5-60 min.
5. The preparation method according to claim 1, further comprising a post-treatment after the spraying, wherein the post-treatment is at least one selected from reduction, electrochemical deposition, electrophoretic deposition and metal evaporation.
6. The method according to claim 1, wherein the electrolytic solution contains at least one of an acid, a base, or a salt;
preferably, the acid is selected from sulfuric acid and/or phosphoric acid; the alkali is selected from potassium hydroxide; the salt is selected from sodium sulfate, lithium chloride, 1-ethyl-3-methylimidazolium tetrafluoroborate and lithium bistrifluoromethanesulfonylimide;
preferably, the electrolyte is selected from any one of a sulfuric acid solution, a phosphoric acid solution, a potassium hydroxide solution, a sodium sulfate solution, a lithium chloride solution, a mixture of sulfuric acid and polyvinyl alcohol, a mixture of phosphoric acid and polyvinyl alcohol, a mixture of potassium hydroxide and polyvinyl alcohol, a mixture of lithium chloride and polyvinyl alcohol, a mixture of sodium sulfate and polyvinyl alcohol, a mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and polyvinylidene fluoride, and a mixture of lithium bistrifluoromethanesulfonimide and polyvinylidene fluoride.
7. A self-powered sensor circuit platform with embedded super capacitor, the self-powered sensor circuit platform with embedded super capacitor comprising: circuit platform Q and embedded ultracapacitor system in circuit platform Q.
8. The supercapacitor embedded self-powered sensor circuit platform according to claim 7, wherein the circuit platform Q comprises a circuit I and a circuit II;
the circuit I and the circuit II are not in contact with each other;
the circuit I is provided with a main circuit A;
the circuit II is provided with a main circuit M;
the branch circuit of the main circuit a and the branch circuit of the main circuit M appear in pairs;
the main circuit A is provided with a branch circuit B 1 ～B x (ii) a And
branch circuit C 1 (ii) a And
branch circuit D 1 ；
The main circuit M has a branch circuit N 1 ～N x Said branch circuit N 1 ～N x And the branch circuit B 1 ～B x As a supercapacitor electrode; and
branch circuit O 1 Said branch circuit O 1 And the branch circuit C 1 For accessing the energy harvesting device 1; and
branch circuit P 1 Said branch circuit P 1 And the branch circuit D 1 For accessing the sensor 1;
the x is a natural number;
preferably, the main circuit A also has a branch circuit C 2 ～C y ，
The main circuit M also has a branch circuit O 2 ～O y Said branch circuit O 2 ～O y And the branch circuit C 2 ～C y Used for accessing energy collecting devices 2-y;
y is an integer greater than 2;
preferably, the main circuit A also has a branch circuit D 2 ～D z ，
The main circuit M also has a branch circuit P 2 ～P z Said branch circuit P 2 ～P z And the branch circuit D 2 ～D z Used for accessing energy sensors 2-z;
z is an integer greater than 2;
preferably, the shape of the main circuit and the branch circuit of the circuit I and the main circuit and the branch circuit of the circuit II is selected from at least one of a segment shape, a curved shape and a zigzag shape.
9. A self-powered sensor, which comprises the self-powered sensor circuit platform with embedded super capacitor prepared by the preparation method of claims 1-6 or the self-powered sensor circuit platform with embedded super capacitor of claims 7-8, an energy collecting device and a sensor, wherein the energy collecting device and the sensor are connected into the self-powered sensor circuit platform with embedded super capacitor.
10. The self-powered sensor of claim 9, wherein the energy harvesting device is selected from at least one of a solar cell, a triboelectric nanogenerator, a piezoelectric nanogenerator;
the sensor is selected from at least one of a mechanical sensor, a temperature sensor, a gas sensor, a humidity sensor and an optical sensor.
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