A bionic flexible electronic film synchronous intelligent sensor and its preparation method

Abstract

The present invention provides a bionic flexible electronic film synchronous intelligent sensor and a preparation method thereof, and relates to the field of flexible intelligent sensing technology. The bionic flexible electronic film synchronous intelligent sensor comprises a main bionic flexible electronic film, and a modified MXene conductive film is introduced by chemical vapor deposition. The present invention provides a bionic flexible electronic film synchronous intelligent sensor and a preparation method thereof. The bionic flexible electronic film multifunctional synchronous intelligent sensor prepared by the method can simultaneously measure temperature, humidity, and pressure sensing performance, and the test processes do not interfere with each other. The flexible sensor integrates three signal test functions, which can reduce the cost and complexity of the sensing system, and demonstrates high sensitivity, fast response recovery rate, long-term sensing stability, and high durability, opening up new paths for applications in the fields of the Internet of Things, flexible electronic skin, and brain-computer interfaces.

Description

Technical Field

[0001] The present invention relates to the field of flexible intelligent sensing technology, in particular to a bionic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. Background Art

[0002] With the increasing demand for portable flexible wearable sensors, the technical research and development of electronic devices with integrated medical detection, monitoring and treatment functions is imminent. Bionic flexible multifunctional sensors have shown great application potential in the fields of brain-computer interaction, electronic skin, smart medical care, and chip-machine humans. What is more exciting is that bionic flexible multifunctional electronic sensor devices have shown irreplaceable application prospects in intraoperative and postoperative cardiac surgery, lung respiration monitoring, and smart gel-controlled sustained-release of drugs, which has also aroused great interest among doctors and patients. Traditional sensing substrates do not fit well with human skin and exhibit disadvantages such as low sensing sensitivity, poor permeability, and poor biocompatibility, making them unsuitable for the manufacture of bionic flexible multifunctional electronic devices specifically for health monitoring and treatment applications.

[0003] Nanocellulose fabrics, with their inherent hygroscopicity, flexibility, comfort, and breathability, are among the most promising candidate materials for constructing biomimetic flexible, wearable, and multifunctional sensing electronics. However, achieving these properties while maintaining their inherent superior performance, along with conductivity, flexibility, biocompatibility, and multifunctional simultaneous sensing capabilities, remains a significant challenge. MXene, a novel conductive material with enhanced mechanical flexibility and ease of film formation, can be used to construct biomimetic flexible conductive thin film sensing layers. Composites of nanocellulose, MXene flexible conductive nanomaterials, conductive polymers, and additives have broad application prospects for biomimetic, flexible, and multifunctional sensing electronics. However, these flexible wearable sensors, designed to measure resistance changes under mechanical stimulation, experience a degree of loss in multifunctional sensing performance, conductivity, durability, and stability during the measurement process, hindering their long-term application in medical monitoring.

[0004] How to simultaneously achieve sustained and stable multifunctional sensing performance, high conductivity, reliable durability and mechanical stability for biomimetic flexible multifunctional sensors used in healthcare and therapeutic fields still faces both scientific and technological challenges. Summary of the Invention

[0005] (1) Technical problems solved

[0006] In response to the shortcomings of the existing technology, the present invention provides a bionic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. The shortcomings of current sensors, such as multi-functional asynchrony, mutual interference of multi-functional sensors, poor self-cleaning ability, low sensitivity, and poor mechanical flexibility, are addressed. The present invention solves the problem that the multi-functional sensing performance, conductivity, durability, and stability of flexible wearable sensors used to measure resistance changes under mechanical stimulation will be lost to a certain extent during the measurement process, making them unable to be used for long-term medical monitoring.

[0007] (2) Technical solution

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0009] A biomimetic flexible electronic film synchronous intelligent sensor, comprising a main biomimetic flexible electronic film and a modified MXene conductive film introduced by chemical vapor deposition. The biomimetic flexible electronic film is prepared by electrospinning using nanocellulose, a conductive polymer, and an additive. The biomimetic flexible electronic film is used to construct a flexible multifunctional synchronous intelligent sensor. The conductive polymer is polyaniline, polypyrrole, or polyphenylene acetylene.

[0010] A flexible composite electronic film is obtained by electrospinning combined with chemical vapor deposition (CVD) to construct a smart sensor, including the following steps:

[0011] S1. A 2-12 w / v% conductive polymer solution containing 10-50% nanocellulose solution was transferred to a 1-15 mL syringe with a needle tip. A modifying agent was then added. The spinning flow rate was set at 0.1-0.8 mm / min. A high voltage of 12-65 kV was applied. The distance between the aluminum foil-coated collector and the needle tip was maintained at 5-70 cm. The collector was rotated at 15-100 rpm to produce a nanocellulose-conductive polymer composite membrane.

[0012] S2. In order to further enhance the conductivity of one side of the nanocellulose-conductive polymer composite membrane, MXene film was modified by introducing it by CVD, and TiO2 nanoparticles were added to the MXene film. The CVD system was pumped at a base pressure of 1-20 Pa, and then 1-70 standard cubic centimeters / minute of H2 and 20-500 cubic centimeters / minute of Ar were used as carrier gases for cleaning. When the expected growth temperature was reached, the growth temperature was 200-900°C, the plasma was turned on, the plasma was 10-200W, and then 1-80 cubic centimeters / minute of CH4 was introduced and CVD was started for reaction. After a period of growth, the plasma was turned off and cooled to room temperature under H2 and Ar conditions to obtain a bionic flexible electronic film multifunctional synchronous intelligent sensor.

[0013] Preferably, the reactants are nanocellulose, a conductive polymer and a modification aid.

[0014] Preferably, the bionic flexible electronic film has a non-interference strategy: when the flexible electronic film is heated, the occurrence rates of the electronic thermoelectric reaction and the ionic thermoelectric reaction are different. The temperature change is measured by the electronic thermoelectric reaction. The greater the temperature difference between hot and cold, the greater the current. The humidity change is measured by the ionic thermoelectric reaction. When the humidity is zero, no ions are transported. When the material is subjected to pressure changes, the resistance decreases and the conductivity increases, thereby detecting the change in reaction pressure.

[0015] Preferably, the bionic flexible electronic film can be used to construct a flexible electronic film multifunctional synchronous intelligent sensor, which is used for real-time detection of synchronous temperature, humidity, and pressure sensing performance. The bionic flexible electronic film synchronous intelligent sensor has high sensitivity, fast response-recovery rate, long-term sensing stability, high durability, high flexibility, and high biocompatibility.

[0016] Preferably, the flexible electronic thin film synchronous intelligent sensor has excellent synchronous sensing performance of temperature, humidity and pressure, and can be widely used in various scenarios such as flexible electronic skin, brain-computer interface, real-time monitoring of vital signs, health care diagnosis, and treatment process monitoring.

[0017] (3) Beneficial effects

[0018] The present invention provides a biomimetic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. It has the following beneficial effects:

[0019] 1. The present invention provides a bionic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. MXene conductive film is introduced by chemical vapor deposition to modify it, and TiO2 nanoparticles are added to the MXene film to further develop a bionic flexible electronic thin film multifunctional synchronous intelligent sensing system. The prepared bionic flexible electronic thin film multifunctional synchronous intelligent sensor exhibits excellent self-cleaning performance, high-sensitivity temperature sensing, high-response humidity sensing, excellent thermal stability, self-heating and bacterial removal performance, as well as outstanding structural reliability and excellent sensing durability. In addition, the bionic flexible electronic thin film multifunctional synchronous intelligent sensor has broad market application prospects in the fields of intelligent medical care and electrotherapy, for example, it shows great potential in flexible electronic skin, real-time medical diagnosis, air disinfection detection, respiratory monitoring, intelligent hot compress, etc.

[0020] 2. The present invention provides a bionic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. The bionic flexible electronic thin film multifunctional synchronous intelligent sensor prepared by this method can simultaneously measure temperature, humidity, and pressure sensing performance, and has a non-interference strategy, so that the test processes do not interfere with each other. In addition, the flexible sensor integrates three signal testing functions, which can reduce the cost and complexity of the sensing system, and demonstrates high sensitivity, fast response-recovery rate, long-term sensing stability, and high durability, opening up new paths for applications in the fields of the Internet of Things, flexible electronic skin, brain-computer interface, etc.

[0021] 3. The present invention provides a bionic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. The bionic flexible electronic thin film synchronous intelligent sensor can be used for synchronous temperature and humidity sensing and pressure sensing, and exhibits high sensitivity, fast recovery-response rate, excellent self-cleaning performance, high biocompatibility, high thermal stability, and extended service life. As a high-tech device, it will provide more convenience to people in future life. It can be implanted on the human body surface as a bionic flexible electronic skin for directly monitoring vital signs including blood pressure, heart rate, body temperature, humidity and other indicators, so as to transmit signals to mobile terminals in a timely manner after vital signs are abnormal.

[0022] 4. The present invention provides a bionic flexible electronic thin film synchronous intelligent sensor and a preparation method thereof. The bionic flexible electronic thin film synchronous intelligent sensor is universal and applicable to most cellulose fabrics. It has the characteristics of rapid large-scale preparation, low cost, good product performance, simple operation, and environmental protection. It has high sensitivity, fast response-recovery rate, long-term sensing stability, high durability, high flexibility, and high biocompatibility. This material is one of the most promising flexible thin film materials for constructing the next generation of bionic flexible intelligent electronic skin. It also has excellent synchronous sensing performance of temperature, humidity, and pressure, and can be widely used in various scenarios such as flexible electronic skin, brain-computer interface, real-time monitoring of vital signs, health and medical diagnosis, and diagnosis and treatment process monitoring. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a schematic structural diagram of the bionic flexible electronic film multifunctional synchronous intelligent sensor of the present invention;

[0024] Figure 2 The sensitivity and recovery-response rate diagram of the bionic flexible electronic film multifunctional synchronous intelligent sensor of the present invention;

[0025] Figure 3 This is a diagram showing the test range of the moisture-sensitive performance of the bionic flexible electronic film multifunctional synchronous intelligent sensor of the present invention;

[0026] Figure 4This is a comparison chart of the humidity-sensing performance of the bionic flexible electronic film multifunctional synchronous intelligent sensor of the present invention;

[0027] Figure 5 This is a SEM image of the bionic flexible electronic film multifunctional synchronous intelligent sensor of the present invention;

[0028] Figure 6 This is a TEM image of the bionic flexible electronic film multifunctional synchronous intelligent sensor of the present invention. DETAILED DESCRIPTION

[0029] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0030] Example 1:

[0031] like Figure 1-3 As shown, an embodiment of the present invention provides a biomimetic flexible electronic film synchronous intelligent sensor, including a main biomimetic flexible electronic film, a modified MXene conductive film introduced by chemical vapor deposition, the biomimetic flexible electronic film is prepared by electrospinning using nanocellulose, a conductive polymer and an additive, the biomimetic flexible electronic film is used to construct a flexible multifunctional synchronous intelligent sensor, and the conductive polymer is polyaniline, polypyrrole or polyphenylene acetylene;

[0032] The flexible composite electronic film is obtained by electrospinning to construct a smart sensor, including the following steps:

[0033] S1. A 5 w / v% polyaniline solution containing 30% nanocellulose solution was transferred to a 10 mL syringe with a needle tip. A modifying agent was then added. The spinning flow rate was set at 0.5 mm / min, a high voltage of 30 kV was applied, and the distance between the aluminum foil-coated collector and the needle tip was maintained at 50 cm. The collector was rotated at 50 rpm to produce a nanocellulose-polyaniline composite membrane.

[0034] S2. In order to further enhance the conductivity of one side of the nanocellulose-polyaniline composite membrane, MXene film was introduced by CVD to modify it, and TiO2 nanoparticles were added to the MXene film. The CVD system was pumped at a base pressure of 8 Pa, and then 40 standard cubic centimeters / minute of H2 and 100 cubic centimeters / minute of Ar were used as carrier gases for cleaning. When the expected growth temperature (500°C) was reached, the plasma was turned on (80W), and then 50 cubic centimeters / minute of CH4 was introduced and CVD was started for reaction. After a period of growth, the plasma was turned off and cooled to room temperature under H2 and Ar conditions to obtain a bionic flexible electronic film multifunctional synchronous intelligent sensor.

[0035] Bionic flexible electronic films can be used to construct flexible electronic film multifunctional synchronous intelligent sensors, which can simultaneously measure three signals: temperature, humidity, and pressure sensing performance. The three sensing test processes do not interfere with each other, reducing the operating difficulty and cost of the circuit system, while improving sensitivity and anti-interference ability. Bionic flexible electronic films have excellent properties such as strong flexibility, high biocompatibility, high sensitivity, fast response-recovery rate, and long-term stability. This provides new ideas for the new application of bionic flexible electronic film multifunctional synchronous intelligent sensors in the combination of flexible electronic skin, brain-computer interface and Internet of Things system.

[0036] from Figure 1 It can be seen that the bionic flexible electronic film multifunctional synchronous intelligent sensor has excellent flexibility, so it can be used for real-time detection of synchronous pressure performance and exhibits high flexibility.

[0037] from Figure 2 It can be seen that the bionic flexible electronic film multifunctional synchronous intelligent sensor demonstrates high sensitivity and fast recovery-response rate during the sensing process. Therefore, it can reflect good long-term sensing stability, high durability, and high biocompatibility, and can provide more convenience to people in future life. It can be implanted on the human body surface as a bionic flexible electronic skin for directly monitoring vital signs including blood pressure, heart rate, body temperature, humidity and other indicators, so that the signal can be transmitted to the mobile terminal in time after the vital signs are abnormal.

[0038] from Figure 3 It can be seen that the bionic flexible electronic film multifunctional synchronous intelligent sensor demonstrates a wide range of humidity sensing performance, and can therefore be used for real-time detection of synchronous temperature and humidity.

[0039] This bionic flexible electronic film has a non-interference strategy: when the flexible electronic film is heated, the occurrence rates of the electronic thermoelectric reaction and the ionic thermoelectric reaction are different. The temperature change is measured by the electronic thermoelectric reaction. The greater the temperature difference between hot and cold, the greater the current. The humidity change is measured by the ionic thermoelectric reaction. When the humidity is zero, no ions are transported. When the material is subjected to pressure changes, the resistance decreases and the conductivity increases, thereby detecting the change in reaction pressure.

[0040] In summary, this bionic flexible electronic thin film synchronous intelligent sensor has excellent synchronous sensing performance of temperature, humidity and pressure, and can be widely used in various scenarios such as flexible electronic skin, brain-computer interface, real-time monitoring of vital signs, health and medical diagnosis, and treatment process monitoring.

[0041] Example 2:

[0042] like Figure 4 As shown, an embodiment of the present invention provides a bionic flexible electronic film synchronous intelligent sensor, including a main bionic flexible electronic film, a modified MXene conductive film introduced by chemical vapor deposition, and the bionic flexible electronic film is prepared by electrospinning using nanocellulose, conductive polymers and additives. The bionic flexible electronic film is used to construct a flexible multifunctional synchronous intelligent sensor, and the conductive polymer is polyaniline, polypyrrole or polyphenylene vinylene.

[0043] The flexible composite electronic film is obtained by electrospinning to construct a smart sensor, including the following steps:

[0044] S1. A 5 w / v% polypyrrole solution or polyphenylene vinylene solution containing 30% nanocellulose solution was transferred to a 10 mL syringe with a needle tip. A modification agent was then added. The spinning flow rate was set at 0.5 mm / min, and a high voltage of 30 kV was applied. The distance between the aluminum foil-coated collector and the needle tip was maintained at 50 cm, and the collector was rotated at 50 rpm to produce a nanocellulose-polypyrrole solution or polyphenylene vinylene composite membrane.

[0045] S2. In order to further enhance the conductivity of one side of the nanocellulose-polypyrrole solution or polyphenylene vinylene composite membrane, MXene film was introduced by CVD to modify it, and TiO2 nanoparticles were added to the MXene film. The CVD system was pumped at a base pressure of 8 Pa, and then 40 standard cubic centimeters / minute of H2 and 100 cubic centimeters / minute of Ar were used as carrier gases for cleaning. When the expected growth temperature (500°C) was reached, the plasma was turned on (80W), and then 50 cubic centimeters / minute of CH4 was introduced and CVD was started for reaction. After a period of growth, the plasma was turned off and cooled to room temperature under H2 and Ar conditions to obtain a bionic flexible electronic film multifunctional synchronous intelligent sensor.

[0046] The conductive polymer used in preparing the flexible electronic sensor is polypyrrole or polyphenylene vinylene.

[0047] from Figure 4 It can be seen that compared with Example 1, the humidity-sensitive performance of the obtained bionic flexible electronic film multifunctional synchronous intelligent sensor has decreased to varying degrees, so it can be seen that the performance of the polyaniline conductive polymer material is better.

[0048] Example 3:

[0049] like Figure 5 As shown, an embodiment of the present invention provides a biomimetic flexible electronic film synchronous intelligent sensor, including a main biomimetic flexible electronic film, a modified MXene conductive film introduced by chemical vapor deposition, and the biomimetic flexible electronic film is prepared by electrospinning using nanocellulose, a conductive polymer, and an additive. The biomimetic flexible electronic film is used to construct a flexible multifunctional synchronous intelligent sensor, and the conductive polymer is polyaniline, polypyrrole, or polyphenylene acetylene;

[0050] The flexible composite electronic film is obtained by electrospinning to construct a smart sensor, including the following steps:

[0051] S1. A 5 w / v% polyaniline solution containing 30% nanocellulose solution was transferred to a 10 mL syringe with a needle tip. A modifying agent was then added. The spinning flow rate was set at 0.5 mm / min, a high voltage of 30 kV was applied, and the distance between the aluminum foil-coated collector and the needle tip was maintained at 50 cm. The collector was rotated at 50 rpm to produce a nanocellulose-polyaniline composite membrane.

[0052] S2. In order to further enhance the conductivity of one side of the nanocellulose-polyaniline composite membrane, MXene film was introduced by CVD to modify it, and TiO2 nanoparticles were added to the MXene film. The CVD system was pumped at a base pressure of 15 Pa, and then 40 standard cubic centimeters / minute of H2 and 100 cubic centimeters / minute of Ar were used as carrier gases for cleaning. When the expected growth temperature (500°C) was reached, the plasma was turned on (80W), and then 50 cubic centimeters / minute of CH4 was introduced and CVD was started for reaction. After a period of growth, the plasma was turned off and cooled to room temperature under H2 and Ar conditions to obtain a bionic flexible electronic film multifunctional synchronous intelligent sensor.

[0053] When preparing the bionic flexible electronic film synchronous intelligent sensor, the CVD system was pumped at a base pressure of 15 Pa.

[0054] from Figure 5It can be seen that compared with Example 1, the thickness of the obtained bionic flexible electronic film increases, and the increase in thickness will lead to partial loss of flexibility. Therefore, it can be known that the bionic flexible electronic film synchronous intelligent sensor has higher requirements for the thickness of the bionic flexible electronic film.

[0055] Example 4:

[0056] like Figure 6 As shown, an embodiment of the present invention provides a biomimetic flexible electronic film synchronous intelligent sensor, including a main biomimetic flexible electronic film, a modified MXene conductive film introduced by chemical vapor deposition, and the biomimetic flexible electronic film is prepared by electrospinning using nanocellulose, a conductive polymer, and an additive. The biomimetic flexible electronic film is used to construct a flexible multifunctional synchronous intelligent sensor, and the conductive polymer is polyaniline, polypyrrole, or polyphenylene acetylene;

[0057] The flexible composite electronic film is obtained by electrospinning to construct a smart sensor, including the following steps:

[0058] S1. A 5 w / v% polyaniline solution containing 30% nanocellulose solution was transferred to a 10 mL syringe with a needle tip. A modifying agent was then added. The spinning flow rate was set at 0.5 mm / min, a high voltage of 30 kV was applied, and the distance between the aluminum foil-coated collector and the needle tip was maintained at 50 cm. The collector was rotated at 50 rpm to produce a nanocellulose-polyaniline composite membrane.

[0059] S2. In order to further enhance the conductivity of one side of the nanocellulose-polyaniline composite membrane, MXene film was introduced by CVD to modify it, and TiO2 nanoparticles were added to the MXene film. The CVD system was pumped at a base pressure of 8 Pa, and then 40 standard cubic centimeters / minute of H2 and 100 cubic centimeters / minute of Ar were used as carrier gases for cleaning. When the expected growth temperature (900°C) was reached, the plasma was turned on (80W), and then 50 cubic centimeters / minute of CH4 was introduced and CVD was started for reaction. After a period of growth, the plasma was turned off and cooled to room temperature under H2 and Ar conditions to obtain a bionic flexible electronic film multifunctional synchronous intelligent sensor.

[0060] The growth temperature when preparing the bionic flexible electronic film synchronous intelligent sensor is set to 900°C.

[0061] from Figure 6 It can be seen that compared with Example 1, the grains on the surface of the obtained biomimetic flexible electronic film are coarser, so it can be known that the higher the growth temperature, the greater the impact on the grain formation of the biomimetic flexible electronic film.

[0062] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a bionic flexible electronic film synchronous intelligent sensor, characterized in that: The bionic flexible electronic film synchronous intelligent sensor comprises a main bionic flexible electronic film, a MXene conductive film is introduced by chemical vapor deposition, the bionic flexible electronic film is prepared by electrostatic spinning using nanocellulose, a conductive polymer and an additive, the bionic flexible electronic film is used to construct a flexible multifunctional synchronous intelligent sensor, and the conductive polymer is polyaniline, polypyrrole or polyphenylene vinylene; The flexible composite electronic film is obtained by electrospinning to construct a smart sensor, including the following steps: S1. A 2-12w / v% conductive polymer solution containing 10-50% nanocellulose solution is transferred to a 1-15mL syringe with a needle tip, and then a modification agent is added. The spinning flow rate is 0.1-0.8mm / min, a high voltage of 12-65kV is applied, and the distance between the collector coated with aluminum foil and the needle tip is maintained at 5-70cm, and the collector is rotated at a speed of 15-100rpm to obtain a nanocellulose-conductive polymer composite film; S2. In order to further enhance the conductivity of one side of the nanocellulose-conductive polymer composite membrane, MXene film was modified by introducing CVD, and TiO2 nanoparticles were added to the MXene film. The CVD system was pumped at a base pressure of 1-20Pa, and then 1-70 standard cubic centimeters / minute of H2 and 20-500 cubic centimeters / minute of Ar were used as carrier gases for cleaning. When the expected growth temperature was reached, the growth temperature was 200-900℃, the plasma was turned on, the plasma was 10-200W, and then 1-80 cubic centimeters / minute of CH4 was introduced and CVD was started for reaction. After a period of growth, the plasma was turned off and cooled to room temperature under H2 and Ar conditions to obtain a bionic flexible electronic film multifunctional synchronous intelligent sensor.

2. The method for preparing a bionic flexible electronic film synchronous intelligent sensor according to claim 1, characterized in that: The reactants are nanocellulose, conductive polymer, MXene film and modification additives.

3. The method for preparing a bionic flexible electronic film synchronous intelligent sensor according to claim 1, characterized in that: The bionic flexible electronic film has a non-interference strategy: when the flexible electronic film is heated, the occurrence rates of the electronic thermoelectric reaction and the ionic thermoelectric reaction are different. The temperature change is measured by the electronic thermoelectric reaction. The greater the temperature difference between hot and cold, the greater the current. The humidity change is measured by the ionic thermoelectric reaction. When the humidity is zero, no ions are transported. When the material receives pressure changes, the resistance decreases and the conductivity increases, thereby detecting the change in reaction pressure.

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