Transient electron conductive ink, method for preparing same, and use thereof

Abstract

This invention belongs to the field of transient electronics, specifically relating to a method for preparing transient electronic conductive ink, comprising the following steps: S1: mixing and grinding ionic fuel and carbon nanotubes to obtain transient electronic ink solid particles; S2: dissolving the solid particles obtained in S1 in a solvent and ultrasonically dispersing them uniformly to obtain a mixed solution; S3: adding graphene to the mixed solution in S2 and ultrasonically stirring; S4: adding ferrocene to the mixed solution obtained in S3 and ultrasonically dispersing it to obtain the transient electronic conductive ink. The transient electronic conductive ink obtained by this preparation method has high conductivity and high energy characteristics, and also has both conductive and self-destructive functions; it can also be automatically and uniformly dispersed in various solvent systems without sedimentation, which is beneficial for storage and use; and it also has high compatibility with flexible electronics fabrication and processing technology, and can be directly printed using existing equipment.

Description

Technical Field

[0001] This invention belongs to the field of transient electronics, specifically relating to a transient electronic conductive ink, its preparation method, and its application. Background Technology

[0002] With the widespread application of electronic devices and information technology, data security and information protection have become increasingly important. This is mainly reflected in two aspects: firstly, the cracking of information storage devices leads to the leakage of confidential information; secondly, the imitation of advanced electronic technologies leads to technological leaks and the loss of technological advantages. Therefore, to prevent data leakage and information theft, transient electronic technology can be used to damage sensitive electronic devices at the hardware level, thereby physically protecting information or destroying out-of-control devices. Unlike the long lifespan and high reliability requirements of general electronic devices, transient electronic devices can operate normally for a period of time, and then, after completing their predetermined tasks or receiving a termination command, they can be partially or completely disintegrated through active or passive triggering.

[0003] Currently, although transient electronics technology has developed to a certain scale, some problems still exist. For example, transient modules are difficult to integrate into microelectronic chips and are incompatible with semiconductor chips; the destruction is incomplete and takes a long time, posing a risk of information leakage; and the transient triggering conditions are harsh, posing a potential risk of transient failure. These defects and problems severely limit transient electronics technology. Therefore, there is an urgent need for a method to prepare a transient electronic conductive ink with high conductivity and energetic properties. Summary of the Invention

[0004] In view of the prior art, the present invention provides a transient electronic conductive ink, its preparation method and application.

[0005] The technical solution adopted in this invention is as follows:

[0006] S1: Ionic fuel and carbon nanotubes are mixed and ground to obtain transient electronic ink solid particles;

[0007] S2: Dissolve the solid particles obtained in S1 in a solvent and disperse them evenly by ultrasonication to obtain a mixed solution;

[0008] S3; Add graphene to the mixed solution of S2 and stir ultrasonically;

[0009] S4: Add ferrocene to the mixed solution obtained in S3, and disperse it by ultrasonication to obtain transient electronic conductive ink.

[0010] Furthermore, the mass ratio of ionic fuel to carbon nanotubes in S1 is 2-3:11, and the grinding time is 20-120 min.

[0011] Furthermore, the ionic fuel in S1 is any one of 1-ethyl-3-methylimidazolium dicyandiamide, 1-propyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazolium dicyandiamide, 1-pentyl-3-methylimidazolium dicyandiamide, 1-ethyl-3-methylimidazolium perchlorate, 1-propyl-3-methylimidazolium perchlorate, 1-butyl-3-methylimidazolium perchlorate, 1-pentyl-3-methylimidazolium perchlorate, 1-ethyl-3-methylimidazolium thiocyanate, 1-propyl-3-methylimidazolium thiocyanate, 1-butyl-3-methylimidazolium thiocyanate, 1-pentyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium nitrate, 1-propyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium nitrate, and 1-pentyl-3-methylimidazolium nitrate.

[0012] Furthermore, the carbon nanotubes in S1 are any one of single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, with a tube length of 200 nm to 2 μm.

[0013] Furthermore, the mass ratio of solid particles to solvent in S2 is 1:1 to 3, the ultrasonic time is 20 min to 60 min, and the stirring time is 30 min to 60 min.

[0014] Furthermore, the solvent in S2 is any one of N,N-dimethylformamide, ethanol, acetone, N-methylpyrrolidone, and methanol.

[0015] Furthermore, the mass ratio of graphene to solid particles in S3 is 1 to 3:10, and the graphene is either single-layer graphene or multi-layer graphene with a size of 100 to 500 nm.

[0016] Furthermore, the mass ratio of ferrocene to solid particles in S4 is 1 to 3:50.

[0017] A transient electronic conductive ink, wherein the conductive ink is a carbon nanotube structure with an energetic coating layer, and the carbon nanotubes overlap to form a three-dimensional conductive network.

[0018] An application of a transient electronic conductive ink, wherein the conductive ink is used to prepare transient electronic devices.

[0019] Technical effect

[0020] (1) The transient electronic ink obtained by the preparation method provided by the present invention has high conductivity and high energy characteristics, and also has both conductivity and self-destruction functions.

[0021] (2) The transient electronic ink obtained by the preparation method provided by the present invention can be automatically and uniformly dispersed in various solvent systems without sedimentation, which is beneficial for preservation and use.

[0022] (3) The transient electronic ink obtained by the preparation method provided by the present invention has high compatibility with flexible electronic fabrication technology and can be directly printed using existing equipment. Attached Figure Description

[0023] Figure 1 This is a physical diagram of the transient electronic ink printing circuit of Embodiment 1 of the present invention.

[0024] Figure 2 This is a physical image of the transient electronic ink of Embodiment 2 of the present invention.

[0025] Figure 3 This is a schematic diagram of the self-destruction of the printing circuit in Embodiment 1 of the present invention.

[0026] Figure 4 This is a SEM image of the electronic ink of Embodiment 3 of the present invention.

[0027] Figure 5 This is a diagram of the actual self-destruction process of the printing circuit in Embodiment 3 of the present invention. Detailed Implementation

[0028] The following will describe in conjunction with embodiments 1-5 of the present invention and appendices. Figure 1-5 The technical solutions of the present invention have been clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] The preparation method of the present invention mainly includes the following steps:

[0030] S1: First, transient electronic ink solid particles are prepared. Ionic fuel and carbon nanotubes are mixed at a mass ratio of 2–3:11 and then fully submerged. The two are bound together by electrostatic attraction between the imidazole cations of the ionic fuel and the π-electron system of the carbon nanotubes. The cation-π interaction involves electron-rich π systems (e.g., benzene, ethylene, acetylene) and adjacent cations (e.g., Li). + Na + Non-covalent molecular interactions between surfaces; this interaction is an example of non-covalent bonding between unipolar (cationic) and tetrapolar (π system); the carbon nanotubes coated with the fuel layer carry the same charge and can be uniformly dispersed in various solvents without sedimentation;

[0031] S2: Dissolve the transient electronic ink solid particles in a solvent, sonicate for 20 min and then stir for 30 min to disperse until uniform. The mass ratio of solid particles to solvent is 1:1 to 3 to obtain a mixed solution.

[0032] S3: Add graphene to the mixed solution of S2, sonicate for 20 min and then stir for 30 min. The mass ratio of graphene to solid particles is 1 to 3:10 to obtain a mixed solution.

[0033] S4: Ferrocene is added to the mixed solution of S3 as a combustion rate catalyst, and the mixture is sonicated for 20 minutes and then stirred for 30 minutes. The mass ratio of ferrocene to solid particles is 1 to 3:50. Ferrocene can effectively improve the energy release efficiency of ink and increase its combustion temperature.

[0034] After obtaining the transient electronic conductive ink, the ink is printed out according to a specific circuit diagram using a pneumatic direct writing method to obtain the transient electronic device. The printing parameters are: speed 0.5-10 mm / s, air pressure 1-50 kPa, and needle size 0.1 mm-2 mm.

[0035] Example 1

[0036] S1: First, 1-ethyl-3-methylimidazolium dicyanamide salt and multi-walled carbon nanotubes with a tube length of 200 nm are mixed at a mass ratio of 2:11 and ground thoroughly for 20 min to obtain solid particles;

[0037] S2: Dissolve solid particles in N,N-dimethylformyl at a mass ratio of 1:1, sonicate for 20 min and then stir for 30 min to obtain a mixed solution.

[0038] S3: Add monolayer graphene with a size of 500 nm to the mixed solution of S2. The mass ratio of graphene to solid particles is 1:10. After sonication for 20 min, stir for 30 min to obtain the mixed solution.

[0039] S4: Add ferrocene to the mixed solution of S3, with a mass ratio of ferrocene to solid particles of 1:50. After sonication for 20 minutes, stir for another 30 minutes to obtain transient electronic conductive ink.

[0040] Transient electronic devices can be obtained by printing the prepared ink according to a specific circuit diagram using a pneumatic direct-write method. The printing parameters are: a travel speed of 1 mm / s, an air pressure of 1 kPa, and a needle size of 0.1 mm. Then, conductivity testing was performed on Example 1. Conductive ink was coated onto a silicon substrate, forming a circuit with a power supply and a light-emitting diode (LED). After power was applied, the LED emitted light, indicating that the conductive ink obtained in Example 1 has good conductivity. Figure 3 A self-destruct test was then performed on Example 1. At 220V, the target chip was completely burned out. Combined with... Figure 1 It is clear that the LEDs and other components in the circuit are functioning normally.

[0041] Example 2

[0042] S1: First, 1-ethyl-3-methylimidazolium perchlorate and single-walled carbon nanotubes with a tube length of 200 nm are mixed at a mass ratio of 2:11 and ground thoroughly for 60 min to obtain solid particles;

[0043] S2: Dissolve solid particles in N,N-dimethylformyl at a mass ratio of 1:2, sonicate for 40 min and then stir for 45 min to obtain a mixed solution.

[0044] S3: Add multilayer graphene to the mixed solution of S2. The size is 500nm. The mass ratio of graphene to solid particles is 2:10. After sonication for 40min, stir for 45min to obtain the mixed solution.

[0045] S4: Add ferrocene to the mixed solution of S3, with a mass ratio of ferrocene to solid particles of 2:50. After sonication for 40 min, stir for another 45 min to obtain transient electronic conductive ink.

[0046] Transient electronic devices can be obtained by printing the prepared ink according to a specific circuit diagram using a pneumatic direct-write method. The printing parameters are: a travel speed of 1 mm / s, an air pressure of 1 kPa, and a needle size of 0.1 mm. Then, a conductivity test was performed on Example 2. Conductive ink was coated on a silicon substrate, forming a circuit with a power supply and a light-emitting diode (LED). After power was applied, the LED emitted light, indicating that the conductive ink obtained in Example 2 has good conductivity. A self-destruct test was then performed on Example 2; at 220V, the target chip was completely burned out. Combined with... Figure 2 middle, Figure 2 'a' represents the initial state of the ink. Figure 2 b represents the state of the ink after one week. Figure 2 As can be seen from b, the ink remained stable and did not undergo a sedimentation process.

[0047] Example 3

[0048] S1: First, 1-ethyl-3-methylimidazolium dicyandiamide salt and single-walled carbon nanotubes with a tube length of 200 nm are mixed at a mass ratio of 2:11 and ground thoroughly for 60 min to obtain solid particles;

[0049] S2: Dissolve solid particles in N,N-dimethylformyl at a mass ratio of 1:3, sonicate for 40 min and then stir for 60 min to obtain a mixed solution.

[0050] S3: Add monolayer graphene with a size of 500 nm to the mixed solution of S2. The mass ratio of graphene to solid particles is 3:10. After sonication for 40 min, stir for 60 min to obtain the mixed solution.

[0051] S4: Add ferrocene to the mixed solution of S3, with a mass ratio of ferrocene to solid particles of 3:50. After sonication for 40 minutes, stir for another 60 minutes to obtain transient electronic conductive ink.

[0052] Transient electronic devices can be obtained by printing the prepared ink according to a specific circuit diagram using a pneumatic direct-write method. The printing parameters are: a travel speed of 2 mm / s, an air pressure of 0.5 kPa, and a needle size of 0.1 mm. Then, a conductivity test was performed on Example 3. Conductive ink was coated on a silicon substrate, forming a circuit with a power supply and a light-emitting diode. After power was applied, the diode emitted light, indicating that the conductive ink obtained in Example 3 has good conductivity. A self-destruct test was then performed on Example 3; at 220V, the target chip was completely burned out. Combined with... Figure 4 The structure and coating of the carbon nanotubes are clearly visible. The carbon nanotubes overlap each other, forming a three-dimensional conductive network. Each carbon nanotube is coated with an energetic coating layer, and these interconnections also form a three-dimensional conductive network. This facilitates normal operation of the circuit under low voltage. Furthermore, the energetic coating layer on the carbon nanotubes allows for effective ignition of the coating layer and release of energy when the carbon nanotubes are stimulated by high voltage, resulting in a short-term temperature increase. Figure 5 It can be seen that the circuit spontaneously combusted and was completely destroyed within 0.6 seconds.

[0053] Example 4

[0054] S1: First, 1-ethyl-3-methylimidazolium nitrate and single-walled carbon nanotubes with a tube length of 200 nm are mixed at a mass ratio of 2:11 and ground thoroughly for 20 min to obtain solid particles;

[0055] S2: Dissolve solid particles in N,N-dimethylformyl at a mass ratio of 1:1, sonicate for 20 min and then stir for 60 min to obtain a mixed solution.

[0056] S3: Add multilayer graphene to the mixed solution of S2. The size is 500nm. The mass ratio of graphene to solid particles is 1:10. After sonication for 40 minutes, stir for another 40 minutes to obtain the mixed solution.

[0057] S4: Add ferrocene to the mixed solution of S3, with a mass ratio of ferrocene to solid particles of 1:50. After sonication for 20 minutes, stir for another 30 minutes to obtain transient electronic conductive ink.

[0058] Transient electronic devices can be obtained by printing the prepared ink according to a specific circuit diagram using a pneumatic direct-write method. The printing parameters are: a movement speed of 1 mm / s, an air pressure of 0.5 kPa, and a needle size of 0.1 mm. Then, a conductivity test was performed on Example 4. Conductive ink was coated on a silicon substrate, forming a circuit with a power supply and a light-emitting diode. After the power was turned on, the diode emitted light, indicating that the conductive ink obtained in Example 4 has good conductivity. A self-destruct test was then performed on Example 4; at 220V, the target chip was completely burned out.

[0059] Example 5

[0060] S1: First, 1-ethyl-3-methylimidazolium nitrate and single-walled carbon nanotubes with a tube length of 200 nm are mixed at a mass ratio of 2:11 and ground thoroughly for 20 min to obtain solid particles;

[0061] S2: Dissolve solid particles in N,N-dimethylformyl at a mass ratio of 1:1, sonicate for 20 min and then stir for 60 min to obtain a mixed solution.

[0062] S3: Add multilayer graphene to the mixed solution of S2. The size is 500nm. The mass ratio of graphene to solid particles is 1:10. After sonication for 40 minutes, stir for another 40 minutes to obtain the mixed solution.

[0063] S4: Add ferrocene to the mixed solution of S3, with a mass ratio of ferrocene to solid particles of 1:50. After sonication for 20 minutes, stir for another 30 minutes to obtain transient electronic conductive ink.

[0064] Transient electronic devices can be obtained by printing the prepared ink according to a specific circuit diagram using a pneumatic direct-write method. The printing parameters are: a movement speed of 1 mm / s, an air pressure of 0.5 kPa, and a needle size of 0.1 mm. Then, a conductivity test was performed on Example 5. Conductive ink was coated on a silicon substrate, forming a circuit with a power supply and a light-emitting diode. After the power was turned on, the diode emitted light, indicating that the conductive ink obtained in Example 5 has good conductivity. A self-destruct test was then performed on Example 5; at 220V, the target chip was completely burned out.

[0065] The present invention provides a method for preparing transient electronic conductive ink, which uses carbon nanotubes as the conductive component in the ink, and then adsorbs electrically sensitive ionic fuel around the carbon nanotubes through cation-π interaction; after polymerization and addition of graphene and ferrocene, the transient electronic conductive ink can be obtained. Then, the ink can be directly processed into electronic circuits through flexible electronic printing technology, so that the circuits have the dual functions of high conductivity and transient damage, realizing the unification of electrical integrated circuits and energetic modules, solving the problem that energetic materials cannot be integrated into MEMS (Micro-Electro-Mechanical Systems) devices. Its preparation time is short, its applicability is wide, and it has good application prospects.

Claims

1. A method for preparing a transient electronically conductive ink, characterized in that, Includes the following steps: S1: Ionic fuel and carbon nanotubes are mixed and ground to obtain transient electronic ink solid particles; the ionic fuel is 1-ethyl-3-methylimidazolium dicyanamide salt, 1-propyl-3-methylimidazolium dicyanamide salt, 1-butyl-3-methylimidazolium dicyanamide salt, 1-pentyl-3-methylimidazolium dicyanamide salt, 1-ethyl-3-methylimidazolium perchlorate, 1-propyl-3-methylimidazolium perchlorate, 1-butyl-3-methylimidazolium perchlorate, etc. The chlorate, 1-pentyl-3-methylimidazolium perchlorate, 1-ethyl-3-methylimidazolium thiocyanate, 1-propyl-3-methylimidazolium thiocyanate, 1-butyl-3-methylimidazolium thiocyanate, 1-pentyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium nitrate, 1-propyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium nitrate, and 1-pentyl-3-methylimidazolium nitrate; S2: Dissolve the solid particles obtained in S1 in a solvent and disperse them evenly by ultrasonication to obtain a mixed solution; S3; Add graphene to the mixed solution of S2, and stir ultrasonically to obtain a mixed solution; S4: Add ferrocene to the mixed solution obtained in S3, and disperse it by ultrasonication to obtain transient electronic conductive ink.

2. The method for preparing a transient electronic conductive ink according to claim 1, characterized in that, The mass ratio of ionic fuel to carbon nanotubes in S1 is 2-3:11, and the grinding time is 20-120 min.

3. The method for preparing a transient electronic conductive ink according to claim 1, characterized in that, The carbon nanotubes in S1 are any one of single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, with a length of 200 nm to 2 μm.

4. The method for preparing a transient electronic conductive ink according to claim 1, characterized in that, The mass ratio of solid particles to solvent in S2 is 1:1 to 3, the ultrasonic time is 20 min to 60 min, and the stirring time is 30 min to 60 min.

5. The method for preparing a transient electronic conductive ink according to claim 1, characterized in that, The solvent in S2 is any one of N,N-dimethylformamide, ethanol, acetone, N-methylpyrrolidone, and methanol.

6. The method for preparing a transient electronic conductive ink according to claim 1, characterized in that, The mass ratio of graphene to solid particles in S3 is 1 to 3:10, and the graphene is either single-layer graphene or multi-layer graphene with a size of 100 to 500 nm.

7. The method for preparing a transient electronic conductive ink according to claim 1, characterized in that, The mass ratio of ferrocene to solid particles in S4 is 1 to 3:

50.

8. A transient electronic conductive ink obtained by the preparation method described in any one of claims 1 to 7.

9. The application of the transient electronic conductive ink according to claim 8, characterized in that, The transient electronic conductive ink is used to prepare transient electronic devices.

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