CN111232959B - Preparation method of miniature graphene aerogel device - Google Patents

Preparation method of miniature graphene aerogel device Download PDF

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CN111232959B
CN111232959B CN202010168736.5A CN202010168736A CN111232959B CN 111232959 B CN111232959 B CN 111232959B CN 202010168736 A CN202010168736 A CN 202010168736A CN 111232959 B CN111232959 B CN 111232959B
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graphene
graphene aerogel
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aerogel
foaming agent
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CN111232959A (en
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许震
高超
庞凯
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Zhejiang University ZJU
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of a micro graphene aerogel device for the first time, the micro-sized graphene aerogel array device is prepared by combining in-situ printing and solution plasticizing and foaming, and the micro-sized graphene aerogel array device has excellent flexibility and stability and can be suitable for various application places such as sensing, energy storage and the like. The array sensor provided by the invention has extremely high stability, so that the array sensor has higher precision and reliability, can be endowed with the function of intelligent learning and identification by combining with deep machine learning, and plays a great role in promoting the development of next generation artificial intelligence.

Description

Preparation method of miniature graphene aerogel device
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method and application of a miniature graphene aerogel device.
Background
With the progress of science and technology, devices tend to be flexible and miniaturized, and at present, miniaturized devices are mainly manufactured by focusing on mature silicon-based CMOS (complementary metal oxide semiconductor) processes, but due to the limited performance, the performance compatibility of the devices in many complex environments is difficult, so that the problem needs to be solved by developing novel materials and processes urgently. Graphene is a nano-carbon material constructed by single-layer carbon atoms in an sp2 hybridization mode, and a conduction band and a valence band of the graphene intersect at a dirac point, so that the graphene has an ultra-fast electron transmission speed, has extremely high electric conduction, thermal conduction and mechanical properties, and is the material most hopeful to solve the problem of miniaturization devices. However, graphene has extremely strong van der waals interaction force, so that the property of a single layer of graphene is maintained in a macroscopic assembly material, and the application of graphene is limited.
The graphene aerogel is formed by a three-dimensional porous network formed by lapping a single layer or few layers of graphene sheets and air, so that the interlayer acting force is weakened by utilizing gaps, the inherent performance of the graphene aerogel can be exerted, and a lot of application researches can be obtained. When the graphene with the nanometer thickness in the material is subjected to weak external stimulation, such as force, electricity, heat, sound and the like, the overall signal of the material is disturbed, so that the detection of various stimulation can be realized; in addition, due to the existence of the porous structure in the graphene aerogel, more transmission channels are provided for charge ions of the graphene aerogel, and therefore the graphene aerogel plays a role in the field of energy storage. However, graphene aerogel is mainly prepared by a freezing template method at present, but because ice crystals are difficult to avoid defects in the freezing and icing process, the performance of the graphene aerogel is greatly reduced, and the subsequent complex template removal also causes that the graphene aerogel is difficult to be subjected to miniaturization, integration and large-scale production.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a micro graphene aerogel device, which mainly utilizes in-situ foaming to obtain a micro-level graphene aerogel unit on a substrate of the device.
Foretell dropwise add can adopt 3D to print and realize, and 3D prints and has high precision, and the miniaturization can be realized to the obtained aerogel array, and the stability of obtained aerogel is comparatively excellent, consequently can obtain the graphite alkene aerogel array sensor that has higher resolution ratio.
Another objective of the present invention is to provide a method for preparing a graphene aerogel device, which mainly combines solvent plasticization and in-situ bubble generation, and the method is different from the existing thermoplastic foaming, in which a plasticizer permeates into a film material in a solution environment, so as to reduce intermolecular force inside the film material and reduce foaming resistance; meanwhile, the foaming problem of non-thermoplastic materials is solved, and the stability of the aerogel device is improved.
In order to achieve any one of the above purposes, the following scheme is adopted in the application: the method comprises the steps of printing a graphene oxide solution on a substrate of a device by using the graphene oxide solution as ink, dripping a polar solution containing a foaming agent after solidification to enable the graphene oxide to be subjected to plasticizing foaming, and drying and reducing to obtain the miniature graphene aerogel unit on the substrate of the device.
Or the following equivalents may be used:
the method comprises the steps of printing a graphene oxide solution doped with a foaming agent on a substrate of a device as ink, solidifying, dropwise adding a polar solution to enable the graphene oxide to be subjected to plasticizing foaming, and drying and reducing to obtain the miniature graphene aerogel unit on the substrate of the device.
The blowing agent includes a self-blowing agent and a reactive blowing agent, the reactive blowing agent is a blowing agent capable of generating gas by reacting with the oxygen-containing functional group of the graphene oxide, and includes, but is not limited to, hydrazine hydrate and borohydride, and the self-blowing agent is a blowing agent capable of decomposing to generate gas, and includes, but is not limited to, bicarbonate.
Methods of initiating the foaming from the blowing agent include, but are not limited to, as is common knowledge in the art: adding an initiator and heating; wherein the initiator initiates the blowing agent precursor to produce a gas.
The polar solution is water, an organic solvent or a mixed solution of water and an organic solvent. The organic solvent is selected from: dimethylformamide, dimethylacetamide, isopropanol, ethanol, and the like. The polar molecules in the polar solution can reduce intermolecular forces of graphene.
The solvent of the graphene oxide solution can be water, dimethylformamide, dimethylacetamide, ethanol, and dimethyl sulfoxide.
In the above method, the drying may be performed in any form, for example, direct drying, solvent replacement drying, and the like.
In some embodiments, before the graphene oxide is printed, a circuit diagram is printed on a substrate of the device to ensure that a circuit lead is positioned below a printed graphene functional unit, which is beneficial to the stability of the device; of course, the method described in the present application may also be performed by printing the graphene oxide ink first, and then further printing the circuit.
Another object of the present invention is to provide a micro graphene aerogel device having extremely high precision, which can be used for a high precision sensitive unit of a micro device.
Another object of the present invention is to provide a graphene aerogel microdevice, which has high stability and is suitable for the field of microdevices requiring long-term stable service.
In order to achieve any one of the above purposes, the following technical scheme is adopted in the application: the miniature graphene aerogel device comprises a plurality of miniature graphene aerogel units, the miniature graphene aerogel units form an array, and the miniature graphene aerogel units can be prepared by adopting a mode of combining in-situ foaming and solvent plasticizing.
The circuit in the device can be designed and processed at will according to requirements, and is a mature technology in the field.
The device can form a sensor, and the miniature graphene aerogel unit is used for data acquisition; the micro graphene aerogel unit is prepared in a mode of combining in-situ foaming and solvent plasticizing, has high responsiveness to mechanical signals, displacement signals and sound wave vibration signals, and can be used for obtaining a high-sensitivity and high-precision sensing control system by combining deep machine learning after the micro graphene aerogel unit forms an array. The deep machine learning can adopt all the programs which can realize data processing, operation, extraction and identification at present.
The device can form a planar energy storage device, and the miniature graphene aerogel unit prepared by combining in-situ foaming and solvent plasticizing has a layer-by-layer orientation structure, so that the miniature capacitor is constructed by utilizing the miniature graphene aerogel unit and has quicker ion transmission capability, and the rate capability of the obtained energy storage device is excellent.
The device can form an energy storage device, and the miniature graphene aerogel unit prepared by combining in-situ foaming and solvent plasticizing has a porous structure, so that the miniature battery is constructed by using the miniature graphene aerogel unit and has high cycling stability.
In the above-mentioned sensors and energy storage devices, circuit design is a technical means mature in the field.
The invention has the beneficial effects that: according to the invention, the micro-sized micro graphene aerogel unit is prepared by combining in-situ printing and solution plasticizing foaming, has excellent flexibility and stability, and can be suitable for various application places such as sensing, energy storage and the like.
The micro-scale device is not limited in size, but can be smaller in size and higher in device precision. The invention is also applicable to the fabrication of large scale devices, but large scale device fabrication is not a primary object of the invention.
The invention has the beneficial effects that: the array sensor provided by the invention has extremely high stability, so that the array sensor has higher precision and reliability, can be endowed with the function of intelligent learning and identification by combining with deep machine learning, and plays a great role in promoting the development of next generation artificial intelligence.
Drawings
FIG. 1 is a schematic view of an 8-arrayed sensor prepared in example 3.
Fig. 2 is a schematic diagram of data collected by the 8-arrayed sensor prepared in example 3.
Fig. 3 is a schematic diagram of an 8-arrayed graphene aerogel sensor prepared in example 4.
FIG. 4 is a graph showing the data change of example 4 at different displacement steps.
Fig. 5 is a schematic diagram of the 10 x 10 arrayed graphene aerogel sensor prepared in example 5.
Fig. 6 is a displacement correction fitted curve of the sensor prepared in example 6.
Fig. 7 is a schematic view of an aluminum nitride piezoelectric resonant sensor used in example 7.
Fig. 8 is a schematic view of the interdigital graphene aerogel capacitor prepared in example 9.
FIG. 9 is a cyclic voltammogram of the capacitor prepared in example 9 at constant scan rate.
FIG. 10 is a graph of capacitance cycling performance of the capacitor prepared in example 9.
Fig. 11 is a schematic view of the lithium ion-graphene aerogel micro-battery prepared in example 10.
Fig. 12 is a graph of capacity and coulombic efficiency maintenance over long time cycles for the cells prepared in example 10.
Fig. 13 is a diagram of recognition of a palm shape by 10 × 10 electrodes according to an application example.
Fig. 14 is a schematic diagram of a highly integrated 8 × 8 finger-arrayed graphene aerogel sensor.
Fig. 15 is a plot of data acquisition for each channel of an 8 by 8 sensor.
Fig. 16 is a schematic diagram of an 8 by 8 array sensor integrated into a robot and controlled by the robot arm.
Fig. 17 is a schematic diagram of a circuit and a principle for performing letter recognition using deep machine learning and a graphene aerogel array sensor.
FIG. 18 is a cross-sectional view taken through the preparation of example 1.
FIG. 19 is a cross-sectional view taken through the preparation of example 2.
Detailed Description
The invention is further described below with reference to examples. The scope of the invention is not limited thereto.
Example 1
Printing on a polyimide substrate by using a 3D printing method by using a graphene oxide aqueous suspension of 20mg/ml as ink, wherein the diameter of a liquid drop is about 20 um; after solidification, 0.1ml of aqueous solution containing 50% hydrazine hydrate is dripped to plasticize and foam graphene oxide, drying is carried out after 5min, and the miniature graphene aerogel unit is obtained after hydriodic acid in-situ reduction.
As shown in fig. 18, it can be seen that graphene aerogel is formed on the polyimide substrate, graphene sheets are overlapped with each other to form a pore structure, and the porosity of the graphene aerogel is almost the same as that of conventional foamed graphene aerogel. The graphene aerogel can be predicted to have the mechanical property, the electrical property, the mechanical and electrical properties and the like of the macroscopic aerogel prepared by the conventional method.
In addition, the graphene aerogel is well combined with the polyimide substrate, and the stability of a device can be effectively guaranteed.
Example 2
And adding sodium bicarbonate with equal mass into a 10mg/ml graphene oxide DMF suspension, and uniformly mixing (the mass ratio of the graphene oxide solution to the sodium bicarbonate is 1: 1) to obtain the graphene oxide ink for 3D printing.
Printing on a transparent PET substrate by using a 3D printing method, wherein the diameter of a liquid drop is about 20 um; and after drying and curing, placing the graphene aerogel in water, heating at 40 ℃ to generate bubbles, drying after 1min, and reducing hydriodic acid in situ to obtain the miniature graphene aerogel unit.
As shown in fig. 19, it can be seen that the PET substrate forms graphene aerogel, graphene sheets are overlapped with each other to form a pore structure, and the porosity of the graphene aerogel is almost the same as that of the conventionally foamed graphene aerogel. The graphene aerogel can be predicted to have the mechanical property, the electrical property, the mechanical and electrical properties and the like of the macroscopic aerogel prepared by the conventional method.
In addition, the graphene aerogel is well combined with the PET substrate, and the stability of the device can be effectively guaranteed.
Example 3
On a polyimide substrate (0.8X 1.0 mm) by means of silk-screen printing2) Sensor circuit diagram printing 8 pairs of electrodes as shown in fig. 1, with single electrode size of 50 x 100um2Each pair ofThe electrodes constitute a test unit. In addition, 8 extraction electrodes and a total electrode are arranged at the bottom; and then 3D printing of graphene oxide ink is carried out on a test unit in a circuit diagram, wherein the graphene oxide solution is 20mg/ml of water suspension, after drying and curing, 0.1ml of hydrazine hydrate aqueous solution with the concentration of 50% is dripped (also dripped by 3D printing means, the same applies below) to carry out in-situ foaming on graphene oxide, after 5min drying, and after in-situ reduction of hydriodic acid, a stable array sensor is obtained, wherein the size of a single miniature graphene aerogel unit is 150 multiplied by 150 um2Inside, and covers the corresponding pair of electrodes.
And leading out the circuit of the 8-electrode sensor into a data acquisition card, connecting the circuit, and inputting 2V test bias voltage to each test unit through the total electrode. The 8 test units are simultaneously pressed by adopting the pressure of 0.2 Pa, and after 8 repeated tests (CH 1-CH 8), the result shows that the current signal is stable, and the response time is 100ms, as shown in figure 2.
The pressure is gradually increased to increase the pressure to 0.4Pa, 0.6Pa, 0.8 Pa, 1.0 Pa, respectively, i.e. a simulated curve is obtained, based on which the force measurement can be performed.
Example 4
Transparent PET substrate (0.8X 1.0 mm) by 3D printing method2) Sensor circuit diagram with 8 pairs of electrodes printed thereon, wherein the individual electrode size is 50 x 100um2In addition, 8 extraction electrodes and a total electrode are arranged at the bottom; and then 3D printing of graphene oxide ink is carried out at each pair of electrodes in a circuit diagram, wherein a graphene oxide solution is 10mg/ml dimethylformamide suspension, 0.1ml sodium borohydride aqueous solution with the concentration of 0.5% is dropwise added after drying and curing so as to carry out in-situ foaming on graphene oxide, drying is carried out after 5min, and a graphene aerogel sensor is obtained after hydriodic acid is subjected to in-situ reduction, wherein the size of each miniature graphene aerogel unit is 150 multiplied by 150 um and 150 um2Inside, and covers the pair of electrodes, as shown in fig. 3.
Leading out the circuit of the 8-electrode sensor into an 8-channel data acquisition card, applying 2V direct current voltage by adopting a zebra paper connecting circuit, and compressing the graphene aerogel by adopting an output probe of a stepping motor. The initial current curve is normalized, signals under different compression quantities are collected, data fitting is carried out, a fitting curve of the compression quantities and current response values can be obtained, fitting data are input into the single chip microcomputer through a program, when each sensor senses different electric signal changes, the electric signal changes can be converted into compression displacement signals in time, and therefore the displacement changes of each sensor are detected, and as shown in fig. 4, obvious signal changes can be observed under continuous displacement progression of 20um, 40um, 60um and 80 um.
Example 5
Printing a sensor circuit diagram of 10 × 10 electrodes on a transparent PET substrate by using a 3D printing method, wherein the size of a single electrode is 1 × 1mm, and then performing 3D printing of graphene oxide ink at a sensing component in the circuit diagram, wherein the graphene oxide ink is a dimethylacetamide suspension of graphene oxide with a concentration of 10mg/ml, after drying and curing, adding 0.2ml of 2% sodium borohydride ethanol solution dropwise by using the 3D printing method to foam the graphene oxide in situ, drying after 5min, and performing in-situ reduction by using hydroiodic acid to obtain a stable aerogel array sensor, wherein the size of a single graphene sensor is 1.5 × 2mm, as shown in fig. 5.
The circuit of the 10 x 10 electrode sensor is led out to a data acquisition card with 8 channels, a zebra paper connecting circuit is adopted, a 2V direct current voltage is applied, when compression is carried out by using different pressures, each sensor has an obvious response signal, and the fact that the prepared sensor can accurately acquire the pressure signals which are not used is verified, the minimum response pressure is 0.32 Pa, and the response time is 120 ms.
Example 6
And adding sodium bicarbonate with equal mass into a 10mg/ml graphene oxide DMF suspension, and uniformly mixing (the mass ratio of the graphene oxide solution to the sodium bicarbonate is 1: 1) to obtain the graphene oxide ink for 3D printing.
Sensor circuit diagram of 8 electrodes printed on transparent PET substrate with single electrode size of 1 by 3D printing method2mm, then 3D printing of graphene oxide ink is carried out on a sensing component in a circuit diagram, after drying and curing, the graphene oxide ink is placed in water, heating is carried out at 40 ℃ to generate bubbles, drying is carried out after 1min, and hydriodic acid is subjected to in-situ reduction to obtain the stable array sensor, wherein the size of a single graphene aerogel sensor is 2 x 4mm2。
Leading out a circuit of the 8-electrode sensor into a data acquisition card, connecting the circuit by adopting zebra paper, applying 2V direct current voltage, compressing the graphene aerogel by adopting an object, normalizing an initial current curve, then acquiring signals under different displacements, and fitting data, wherein as shown in figure 6, a fitting curve of object displacement and current response values can be obtained, the strain sensitivity (GF) of the fitting curve can reach 2 at most, inputting the fitting data into a single chip microcomputer through a program, and when each sensor senses different electric signal changes, the fitting curve can be converted into displacement signals in time, so that the displacement change of each object can be detected.
Example 7
Using a commercial aluminum nitride piezoelectric resonant sensor, as shown in fig. 7, printing a vibration component of 200 × 200um to perform 3D printing of graphene oxide ink, where the graphene oxide ink is an ethanol suspension of graphene oxide with a concentration of 100mg/ml, drying and curing, dropping 0.3ml of 20% hydrazine hydrate solution in dimethylformamide by using a 3D printing method to foam the graphene oxide in situ, drying after 5min, and performing in-situ reduction with hydriodic acid to obtain a stable array sensor, where the size of a single graphene aerogel sensor is 300 × 300um2。
The sensor can be used for manufacturing a passive sound wave detection system. When a sound wave with a certain frequency occurs (within the bandwidth of the piezoelectric resonator, generally below 1 MHz), the piezoelectric film generates periodic vibration (hundred-nanometer amplitude), due to the positive piezoelectric effect, an induced current (microampere level) with a corresponding frequency is generated by periodic strain, and the electrical characteristic change of the graphene aerogel on the resonator amplifies an electrical signal (decamicroampere level). The induced current is respectively collected at the upper electrode and the lower electrode and is connected to the circuit board in a lead bonding mode. The signal can be detected (amplified to milliamp level) through a power amplification circuit and a filter circuit. From the frequency and amplitude information of the signal, information such as the frequency and intensity of the sound wave can be extracted.
Example 8
3D printing of graphene oxide ink is carried out at a vibration component of a commercial aluminum nitride piezoelectric resonant sensor, wherein the graphene oxide ink is dimethylacetamide suspension of graphene oxide with the concentration of 10mg/ml, after drying and solidification, 0.3ml of dimethylacetamide/water (1: 1 wt/wt) solution with the concentration of 20mg/ml is dripped by using a 3D printing method to carry out in-situ foaming on the graphene oxide, drying is carried out after 5min, and hydriodic acid is subjected to in-situ reduction to obtain a stable array sensor, wherein the size of a single graphene aerogel unit is 500 x 500um2。
The sensor can be used for manufacturing a mechanical and displacement detection system, the piezoelectric device has periodic vibration (hundred-nanometer amplitude), and when a very small mechanical or strain signal appears, the electrical signal of the aerogel changes, and can be amplified by 10-100 times through signal amplification of the vibration device, so that the sensor has very high detection precision. The minimum detection pressure was 0.001Pa and the minimum detection displacement was 0.01%.
Example 9
Printing an interdigital silver circuit diagram of 10 × 10 electrodes on a transparent PET substrate by using a 3D printing method as a current collector, as shown in FIG. 8, wherein the size of a single electrode is 20 × 1mm, and then performing 3D printing of graphene oxide ink at an electrode part in the circuit diagram, wherein the graphene oxide solution is DMF suspension of graphene oxide with the concentration of 15mg/ml, after drying and curing, 0.2ml of sodium borohydride isopropyl acetamide propanol solution with the concentration of 4% is dripped by using the 3D printing method to foam the graphene oxide in situ, after 5min drying, and after hydroiodic acid in situ reduction, a stable array micro-capacitor is obtained, wherein the size of a single graphene unit is 20 × 1mm2。
The method comprises the steps of printing 10 interdigital capacitors, then connecting the interdigital capacitors in series, leading electrodes at two ends out of an electrochemical workstation, and when cyclic voltammetry tests are carried out at different scanning speeds, finding that the interdigital capacitors have obvious capacity of capacity storage, such as fig. 9, have large instantaneous output voltage, such as 10V, can be cycled and stabilized for 10000 times, and have no obvious capacity reduction, such as fig. 10, and proving that the micro-array supercapacitor has great potential application value in the future micro-electronic field.
Example 10
Printing interdigitated silver circuit patterns of two pairs of 3 x 3 electrodes on a transparent PET substrate using a 3D method in parallel as current collectors using commercial carbon coated Li4Ti5O12Printing the particles on one end of the interdigital electrode to be used as an anode material; printing 60mg/ml of graphene oxide dimethyl sulfoxide suspension on a cathode, drying, dropwise adding 0.1ml of 25% hydrazine hydrate isopropanol solution by using a 3D printing method to foam the graphene oxide dimethyl sulfoxide suspension in situ, drying after 5min, and reducing hydroiodic acid in situ to obtain the stable array lithium ion battery, as shown in figure 11, wherein the stable array lithium ion battery has ultrahigh energy density which can reach 59.8 mWh-cm-3The porous aerogel structure can greatly increase the electron transmission speed of the electrolyte, accelerate the charge and discharge speed, and basically keep the capacitance and the coulombic efficiency unchanged after 5000 times of charge and discharge, as shown in figure 12, the rate capability of the prepared micro battery is better.
Application example 1
Preparation of electrodes a 10 x 10 aerogel array as shown in example 5 was attached to two 64 channel data acquisition cards to simultaneously acquire 100 channel signals, and when the palm was pressed down on the aerogel array, a clear hand shape was observed by data processing, as shown in fig. 13.
Application example 2
A sensor circuit diagram of 8 × 8 electrodes is printed on a polyimide substrate by using an FCT process, the size of a single aerogel electrode is 300 × 400um, and then 3D printing of graphene oxide ink is performed at a sensing component in the circuit diagram, wherein a graphene oxide solution is 20mg/ml of water suspension, after drying and curing, 0.1ml of hydrazine hydrate aqueous solution with the concentration of 50% is added dropwise to foam graphene oxide in situ, and after 5min drying, hydriodic acid is reduced in situ to obtain a stable array sensor, as shown in fig. 14.
The circuit of the 8-by-8 electrode sensor is led out to a single chip microcomputer, a wire is connected with the circuit, data are collected by a round reading method, and as shown in fig. 15, all the sensors have obvious response signals. Fixing the prepared sensor on the finger of a dexterous hand, driving by using a mechanical arm, respectively pressing 26 letters as shown in figure 16, and inputting the obtained data into a computer convolution neural network for deep learning; after the trained neural network is obtained, different letters are randomly selected and pressed by a dexterous hand, the unknown letters can be quickly recognized within 1s, the recognition accuracy rate is far higher than the recognition rate (30 percent) of human fingers and can reach 100 percent, and a specific machine learning schematic diagram is shown in figure 17.

Claims (12)

1. A method for preparing a miniature graphene aerogel device, wherein the device comprises miniature graphene aerogel units, and the method is characterized by comprising the following steps: the method comprises the steps of printing a graphene oxide solution on a substrate of a device by using the graphene oxide solution as ink, dripping a polar solution containing a foaming agent after solidification to enable the graphene oxide to be subjected to plasticizing foaming, and drying and reducing to obtain the miniature graphene aerogel unit on the substrate of the device.
2. The method of claim 1, wherein: the foaming agent comprises a self-foaming agent and a reaction type foaming agent, wherein the reaction type foaming agent can generate gas through reaction with the oxygen-containing functional group of the graphene oxide, and the self-foaming agent can be decomposed to generate gas.
3. The method of claim 2, wherein: the reactive foaming agent is hydrazine hydrate or borohydride; the self-foaming agent comprises bicarbonate.
4. The method according to claim 1, characterized in that: the polar solution containing the foaming agent is water containing the foaming agent, an organic solvent or a mixed solution of water and the organic solvent.
5. The method according to claim 4, wherein: the organic solvent is selected from: one or more of dimethylformamide, dimethylacetamide, isopropanol and ethanol.
6. The method of claim 1, wherein: the solvent of the graphene oxide solution is one or more of water, dimethylformamide, dimethylacetamide, ethanol and dimethyl sulfoxide.
7. The method of claim 1, wherein a circuit pattern is printed on the substrate of the device before the graphene oxide is printed.
8. A micro graphene aerogel device, comprising a plurality of micro graphene aerogel cells according to claim 1, wherein the plurality of micro graphene aerogel cells form an array.
9. The micro graphene aerogel device of claim 8, wherein the device is a piezoresistive sensor, wherein mechanical or displacement data signal acquisition is performed by the micro graphene aerogel cells.
10. The graphene aerogel micro-device of claim 8, wherein the device is a resonant sensor, and wherein the micro graphene aerogel unit is used for mechanical signal acquisition, displacement signal acquisition or acoustic vibration signal acquisition.
11. The microshpene aerogel device of claim 8, wherein the device is an energy storage device, wherein a microcapacitor is constructed using microshpene aerogel cells.
12. The graphene aerogel micro-device of claim 8, wherein the device is an energy storage device, and wherein a micro battery is constructed using the graphene aerogel micro-cells and metal electrodes.
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