MINIATURE GRAPHENE AEROGEL DEVICE AND PREPARATION METHOD THEREOF

Abstract

Disclosed are a preparation method for a graphene aerogel array sensor and use thereof. A miniature graphene aerogel array device is prepared by combining in-situ printing and solvent plasticization and foaming, which has excellent flexibility and stability, and is suitable for use in a variety of scenarios, such as sensors, and energy storage devices, etc. The array sensor provided in the present disclosure exhibites extremely high stability, high accuracy and reliability. Combining with deep machine learning, the array sensor can be endowed with the function of learning and recognition of machine intelligence, thus greatly promoting the development of the next generation of artificial intelligence.

Claims

1. A method for preparing a miniature graphene aerogel device having a miniature graphene aerogel unit, the method comprising: printing on a substrate of a device with a graphene oxide solution as an ink, dripping a polar solution containing a foaming agent after solidifying to plasticize and foam the graphene oxide, drying and reducing to obtain a miniature graphene aerogel unit on the substrate of the device.

2. The preparation method according to claim 1, wherein the foaming agent comprises a self-foaming agent or a reactive foaming agent, wherein the reactive foaming agent is a foaming agent that reacts with an oxygen-containing functional group of graphene oxide to produce a gas, and the self-foaming agent is a foaming agent that decomposes to produce a gas.

3. The preparation method according to claim 2, wherein the reactive foaming agent comprises hydrazine hydrate, and a borohydride; and the self-foaming agent comprises a bicarbonate.

4. The preparation method according to claim 1, wherein the polar solution comprises water, an organic solvent, or a mixed solution of water and an organic solvent.

5. The preparation method according to claim 4, wherein the organic solvent is selected from: dimethylformamide, dimethylacetamide, isopropanol, and ethanol.

6. The preparation method according to claim 1, wherein the solvent in the graphene oxide solution is water, dimethyl formamide, dimethyl acetamide, ethanol, or dimethyl sulfoxide.

7. The preparation method according to claim 1, wherein a circuit is printed on the substrate of the device before printing the graphene oxide.

8. A miniature graphene aerogel device, comprising multiple miniature graphene aerogel units in an array.

9. The miniature graphene aerogel device according to claim 8, which is a piezoresistive sensor, wherein the miniature graphene aerogel unit acquires mechanical and displacement data signals.

10. The miniature graphene aerogel device according to claim 9, wherein the sensor is a resonant sensor, wherein the miniature graphene aerogel unit acquires mechanical signals, displacement signals, and acoustic vibration signals.

11. The miniature graphene aerogel device according to claim 8, which is an energy storage device, wherein the miniature graphene aerogel unit is configured to form a miniature capacitor.

12. The miniature graphene aerogel device according to claim 8, which is an energy storage device, wherein the miniature graphene aerogel unit is configured to form a miniature battery together with a metal electrode.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 is a schematic view of an 8-electrode array sensor prepared in Example 3.

[0029] FIG. 2 is a schematic view showing the data acquired by the 8-electrode array sensor prepared in Example 3.

[0030] FIG. 3 is a schematic view of an 8-electrode array graphene aerogel sensor prepared in Example 4.

[0031] FIG. 4 shows the data change curve of Example 4 with different displacement steps.

[0032] FIG. 5 is a schematic view of a 10*10 array graphene aerogel sensor prepared in Example 5.

[0033] FIG. 6 shows a displacement calibration fitting curve of a sensor prepared in Example 6.

[0034] FIG. 7 is a schematic view of an aluminum nitride piezoelectric resonant sensor used in Example 7.

[0035] FIG. 8 is a schematic view of an interdigital miniature graphene aerogel capacitor prepared in Example 9.

[0036] FIG. 9 shows a cyclic voltammetry curve of the capacitor prepared in Example 9 at a constant scanning speed.

[0037] FIG. 10 shows a cycle performance curve of the capacitor prepared in Example 9.

[0038] FIG. 11 is a schematic view of a lithium ion-graphene aerogel miniature battery prepared in Example 10.

[0039] FIG. 12 shows the capacitance and coulombic efficiency retention rate of the battery prepared in Example 10 during a long-term cycle process.

[0040] FIG. 13 is a view showing the recognition of a palm shape by a 10*10 electrode in an application example.

[0041] FIG. 14 is a schematic view of a highly integrated 8*8 finger array graphene aerogel sensor.

[0042] FIG. 15 shows a data acquisition curve of each channel of an 8*8 sensor.

[0043] FIG. 16 is a schematic view of an 8*8 array sensor integrated in a manipulator and controlled by the manipulator.

[0044] FIG. 17 is a schematic view showing a circuit capable of letter recognition by using deep machine learning and a graphene aerogel array sensor, and an underlying principle thereof.

[0045] FIG. 18 is a cross-sectional view of a graphene aerogel device prepared in Example 1.

[0046] FIG. 19 is a cross-sectional view of a graphene aerogel device prepared in Example 2.

DESCRIPTION OF THE EMBODIMENTS

[0047] The present disclosure will be further described below with reference to embodiments. However, the protection scope of the present disclosure is not limited thereto.

Example 1

[0048] A 20 mg/ml graphene oxide aqueous suspension as an ink was printed on a polyimide substrate by 3D printing, with a droplet diameter being about 20 μm. After solidification, 0.1 ml of an aqueous solution containing 50% hydrazine hydrate was dripped, to plasticize and foam the graphene oxide. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a miniature graphene aerogel unit.

[0049] The cross section of the polyimide substrate was observed. As shown in FIG. 18, it can be seen that a graphene aerogel is formed on the polyimide substrate, and the graphene sheets are overlapped on each other to form a porous structure, with a porosity comparable to that of a conventional foamed graphene aerogel. It is expected that this graphene aerogel possesses the mechanical properties, electrical properties, and electromechanical properties, etc. of macroscopic aerogels prepared by a conventional method.

[0050] In addition, the graphene aerogel is well connected with the polyimide substrate, which can effectively guarantee the stability of the device.

Example 2

[0051] A 10 mg/ml suspension of graphene oxide in DMF was added with an equal weight of sodium bicarbonate and mixed uniformly (where the weight ratio of the graphene oxide solution to sodium bicarbonate was 1:1) to obtain a graphene oxide ink for 3D printing.

[0052] The graphene oxide ink was printed on a transparent PET substrate by 3D printing, with a droplet diameter being about 20 μm. After drying and solidification, the product was placed in water, heated at 40° C. to generate bubbles, then dried after 1 min, and subjected to in-situ reduction with hydroiodic acid to obtain a miniature graphene aerogel unit.

[0053] The cross section of the PET substrate was scanned. As shown in FIG. 19, it can be seen that a graphene aerogel is formed on the PET substrate, and the graphene sheets are overlapped on each other to form a porous structure, with a porosity comparable to that of a conventional foamed graphene aerogel. It is expected that this graphene aerogel possesses the mechanical properties, electrical properties, and electromechanical properties, etc. of macroscopic aerogels prepared by a conventional method.

[0054] In addition, the graphene aerogel is well connected with the PET substrate, which can effectively guarantee the stability of the device.

Example 3

[0055] A sensor circuit of 8 pairs of electrodes as shown in FIG. 1 was printed on a polyimide substrate (0.8×1.0 mm.sup.2) by screen printing. The size of a single electrode is 50×100 μm.sup.2, and each pair of electrodes constitutes a test unit. In addition, 8 extraction electrodes and 1 common electrode were set at the bottom. Then, a graphene oxide ink was printed on the test unit in the circuit by 3D printing, in which the graphene oxide ink is a 20 mg/ml aqueous suspension. After drying and solidification, 0.1 ml of an aqueous solution containing 50% hydrazine hydrate was dripped (also by 3D printing, the same below), to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable array sensor. An individual miniature graphene aerogel unit has a size within 150×150 μm.sup.2, and is covered on a corresponding pair of electrodes.

[0056] The circuit of the 8-electrode sensor was led to a data acquisition card, the circuit was connected, and a 2V test bias voltage was input to each test unit through the common electrode. A pressure of 0,2 Pa was applied to the 8 test units at the same time. After 8 repeated tests (CH1-CH8), the results show that the current signal is stable and the response time is 100 ms, as shown in FIG. 2.

[0057] The pressure was gradually increased to 0.4 Pa, 0.6 Pa, 0.8 Pa, and 1.0 Pa, and then a simulation curve was obtained. Force measurement can be performed based on the simulation curve.

Example 4

[0058] A sensor circuit of 8 pairs of electrodes was printed on a transparent PET substrate (0.8×1.0 mm.sup.2) by 3D printing, where the size of a single electrode is 50×100 μm.sup.2. In addition, 8 extraction electrodes and 1 common electrode were set at the bottom. Then, a graphene oxide ink was printed on each pair of electrodes in the circuit by 3D printing, in which the graphene oxide ink is a 10 mg/ml suspension in dimethyl formamide. After drying and solidification, 0.1 ml of an aqueous solution containing 0.5% sodium borohydride was dripped, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a graphene aerogel sensor. Each miniature graphene aerogel unit has a size within 150×150 um.sup.2, and is covered on a pair of electrodes, as shown in FIG. 3.

[0059] The circuit of the 8-electrode sensor was led to an 8-channel data acquisition card, and the circuit was connected by a heat seal connector. A 2V DC voltage was applied, and the graphene aerogel was compressed by an output probe of a stepping motor. The initial current curve was normalized, and then the signals were acquired at different compression levels. The data was fitted, to obtain a fitting curve of the current response value vs the compression level. The fitted data was input into a single-chip microcomputer by a program. When a different electrical signal change is sensed by each sensor, it can be converted into a compression displacement signal in time to detect the displacement change of each sensor, as shown in FIG. 4. An obvious signal change can be observed with continuous progressive displacement of 20 μm, 40 μm, 60 μm and 80 μm.

Example 5

[0060] A sensor circuit of 10*10 electrodes was printed on a transparent PET substrate by 3D printing, where the size of a single electrode is 1*1 mm. Then, a graphene oxide ink was printed on the sensor component in the circuit by 3D printing, in which the graphene oxide ink is a 10 mg/ml suspension of graphene oxide in dimethyl acetamide. After drying and solidification, 0.2 ml of 2% sodium borohydride solution in ethanol was dripped by 3D printing, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable array sensor. An individual graphene aerogel sensor has a size of 1.5*2 mm, as shown in FIG. 5.

[0061] The circuit of the 10*10-electrode sensor was led to an 8-channel data acquisition card, and the circuit was connected by a heat seal connector. A 2V DC voltage was applied. When pressed under various pressures, each sensor was found to have an obvious response signal, it indicates that the prepared sensor can accurately acquire different pressure signals, with a minimum response pressure of 0.32 Pa and a response time of 120 ms.

Example 6

[0062] A 10 mg/ml suspension of graphene oxide in DMF was added with an equal weight of sodium bicarbonate and mixed uniformly (where the weight ratio of the graphene oxide solution to sodium bicarbonate was 1:1) to obtain a graphene oxide ink for 3D printing.

[0063] A sensor circuit of 8 electrodes was printed on a transparent PET substrate by 3D printing, where the size of a single electrode is 1*2 mm. Then, a graphene oxide ink was printed on the sensor component in the circuit by 3D printing. After drying and solidification, the sensor circuit was placed in water, and heated at 40° C. to generate bubbles. After 1 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable array sensor. An individual graphene aerogel sensor has a size of 2*4 mm.sup.2.

[0064] The circuit of the 8-electrode sensor was led to a data acquisition card, and the circuit was connected by a heat seal connector. A 2V DC voltage was applied, and the graphene aerogel was pressed by an object. The initial current curve was normalized, and then the signals were acquired at different displacements. The data was fitted, to obtain a fitting curve of the current response value vs the displacement of the object, as shown in FIG. 6. The gauge factor (GF) can reach 2. The fitted data was input into a single-chip microcomputer by a program. When a different electrical signal change is sensed by each sensor, it can be converted into a displacement signal in time to detect the displacement change of each object.

Example 7

[0065] A commercial aluminum nitride piezoelectric resonant sensor as shown in FIG. 7 was used. A graphene oxide ink was printed on a vibration component of 200*200 um by 3D printing, in which the graphene oxide ink is a 100 mg/ml suspension of graphene oxide in ethanol. After drying and solidification, 0.3 ml of a 20% hydrazine hydrate solution in dimethyl formamide was dripped by 3D printing, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable array sensor. An individual graphene aerogel sensor has a size of 300*300 um.sup.2.

[0066] The sensor can be prepared into a passive acoustic wave detection system. When an acoustic wave of a certain frequency appears (within the bandwidth of the piezoelectric resonator, generally below 1 MHz), the piezoelectric film periodically vibrates (with an amplitude of hundreds of nanometers). Due to the positive piezoelectric effect, the periodic strain produces an induced current (at microampere level) of corresponding frequency, and the change in the electrical characteristics of the graphene aerogel on the resonator amplifies the electrical signal (ten-microampere level). The induced current is acquired on the upper and lower electrodes respectively and connected to the circuit board by wire bonding. The signal can be detected by a power amplifier circuit and a filter circuit (where it is amplified to milliampere level). According to the frequency and amplitude information of the signal, information such as the frequency and intensity of the acoustic wave can be extracted.

Example 8

[0067] A commercial aluminum nitride piezoelectric resonant sensor was used. A graphene oxide ink was printed on a vibration component by 3D printing, in which the graphene oxide ink is a 100 mg/ml suspension of graphene oxide in dimethyl acetamide. After drying and solidification, 0.3 ml of a 20 mg/ml dimethyl acetamide/water (1:1 wt/wt) solution was dripped by 3D printing, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable array sensor. An individual graphene aerogel unit has a size of 500*500 um.sup.2.

[0068] The sensors can be prepared into a mechanical and displacement detection system. The piezoelectric device can vibrate periodically (with an amplitude of hundreds of nanometers). When a very small mechanical or strain signal appears, the electrical signal of the aerogel changes and the signal transmitted through the vibration component is amplified by 10 to 100 times, resulting in an extremely high detection accuracy. The minimum detection pressure is 0.001 Pa, and the minimum detection displacement is 0.01%.

Example 9

[0069] As shown in FIG. 8, an interdigital silver circuit of 10*10 electrodes was printed as a current collector on a transparent PET substrate by 3D printing, where the size of a single electrode is 20*1 mm. Then, a graphene oxide ink was printed on the electrode component in the circuit by 3D printing, in which the graphene oxide ink is a 15 mg/ml suspension of graphene oxide in DMF. After drying and solidification, 0.2 ml of 4% sodium borohydride solution in dimethyl acetamide/isopropanol was dripped by 3D printing, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable miniature array capacitor. An individual graphene aerogel unit has a size of 20*1 mm.sup.2.

[0070] 10 interdigital capacitors as described above were printed, and then connected in series; and two terminal electrodes were led to an electrochemical workstation. When the capacitors were tested by cyclic voltammetry at different scanning speeds, they were found to have obvious capacitance storage capacity, and have a large instantaneous output voltage that is up to 10 V, as shown in FIG. 9. The capacitors can be stably cycled for 10,000 times without any significant drop in capacitance, as shown in FIG. 10. This proves that such miniature array supercapacitors have extremely huge potential applications in the field of microelectronics in the future.

Example 10

[0071] An interdigital silver circuit of two pairs of 3*3 electrodes was printed and connected in parallel as a current acquireor on a transparent PET substrate by 3D printing. Commercial carbon-coated Li.sub.4Ti.sub.5O.sub.12 particles were printed on one end of the interdigital electrode and used as an anode material. A 60 mg/ml suspension of graphene oxide in dimethyl sulfoxide was printed on the cathode. After drying, 0.1 ml of a 25% hydrazine hydrate solution in isopropanol was dripped by 3D printing, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable lithium-ion array battery as shown in FIG. 11. The battery has an ultra-high energy density of up to 59.8 mWh.Math.cm.sup.−3, in which the porous aerogel structure can greatly increase the carrier transport of the electrolyte and enhance the charging and discharging speed. After 5000 cycles of charge and discharge, the capacitance and coulombic efficiency are kept basically unchanged, as shown in FIG. 12. The rate performance of the prepared miniature battery is good.

Application Example 1

[0072] The preparation of the electrode was as described for the 10*10 aerogel array shown in Example 5. The electrode was connected to two 64-channel data acquisition cards to acquire signals in 100 channel at the same time. When a palm was lowered and pressed on the aerogel array, an obvious hand shape can be observed after data processing, as shown in FIG. 13.

Application Example 2

[0073] A sensor circuit of 8*8 electrodes was printed on a polyimide substrate by the FCT process, where the size of a single aerogel electrode is 300*400 um. Then, a graphene oxide ink was printed on the sensor component in the circuit by 3D printing, in which the graphene oxide ink is a 20 mg/ml aqueous suspension. After drying and solidification, 0.1 ml of 50% aqueous hydrazine hydrate solution was dripped, to foam the graphene oxide in situ. After 5 min, the foamed graphene oxide was dried, and subjected to in-situ reduction with hydroiodic acid to obtain a stable array sensor, as shown in FIG. 14.

[0074] The circuit of the 8*8 electrode sensor was led to a single-chip microcomputer, and the circuit was connected by a wire. Data was acquired by wheel reading. As shown in FIG. 15, all the sensors are confirmed to have obvious response signals. The prepared sensor was fixed on a finger of a dexterous robot hand, and driven to move by a manipulator to press 26 letters respectively, as shown in FIG. 16. The obtained data was input into a convolutional neural network for deep learning. A trained neural network was obtained. Then, different letters are selected at will and pressed by the dexterous robot hand, by which the unknown letters can be recognized quickly within 1 s. The recognition accuracy can reach 100%, which is much higher than the recognition rate of human fingers (about 30%). The specific machine learning is schematically shown in FIG. 17.