CN114076785B - Sensor based on MXene/silk fibroin material and preparation method and application thereof - Google Patents
Sensor based on MXene/silk fibroin material and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to a sensor based on an MXene/silk fibroin composite material and a preparation method thereof, wherein the sensor consists of an MXene/silk fibroin film sensing layer and an MXene interdigital electrode, has the advantages of good flexibility, good air permeability, complete degradation, environmental protection, wide sensing range, high sensitivity, quick response/recovery time, reliable air permeability and excellent cycling stability, can be used for ultra-sensitive pressure sensing and motion positioning, and has great application prospect in the fields of intelligent electronic skin, human motion detection, clinical diagnosis and human-computer interaction.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a sensor based on an MXene/silk fibroin material, and a preparation method and application thereof.
Background
Flexible wearable lightweight pressure sensors have attracted great attention in applications such as wearable electronic skin, flexible touchable displays, human health monitoring, etc. due to their high flexibility, reliable wearability, stable repeatability, excellent sensing performance. The pressure sensors developed according to different sensing mechanisms are different, wherein the piezoresistive sensor composed of a flexible matrix and a conductive material is widely researched due to the advantages of high sensitivity, high response speed, reliable stability and the like, and has a great application prospect in the direction of a new generation of pressure sensors. (H.N. Alshareef, et al, MXene Printing and Patterned Coating for Device Applications, advanced Materials,2020,32,1908486)
MXene(Ti 3 C 2 T x ) Is a newly developed two-dimensional (2D) lamellar transition metal carbo/nitride, which is widely used in the material field due to its high conductivity, large specific surface area and excellent mechanical properties. The surface of the MXene has various groups such as fluorine atoms, oxygen atoms, hydroxyl groups and the like, so that the MXene has excellent hydrophilic property, can be uniformly dispersed in water, is easy to prepare the MXene ink, and is suitable for various processing technologies such as spraying, spin coating, vacuum filtration, screen printing and the like. These excellent properties make it widely applicable to a variety of flexible electronic devices. Meanwhile, the material has wide prospect in the field of sensing materials, and the single-layer MXene with high specific surface area can greatly improve the polymer baseAdhesion of the substrate, which promotes excellent cycle stability, has great potential for industrialization. (Y.H.Gao, et al A Highly Flexible and Sensitive Piezoresistive Sensor Based on MXene with Greatly Changed Interlayer Distances [ J)].Nature Communications,2017,8(1):1-8)
The traditional pressure sensor adopts an airtight elastomer or a compact semiconductor film as a matrix (X.Y.Liu, W.X.Guo, et al, A Biodegradable and Stretchable Protein-Based Sensor as Artificial Electronic Skin for Human Motion Detection [ J ]. Small,2019,15 (11). 1805084), and pores are often blocked and even skin problems are caused by airtight adhesion to skin. On the other hand, as the demand for electronic devices increases, a large amount of electronic waste is generated during the complex substrate manufacturing and slow degradation of the devices, and serious environmental pollution is caused due to toxic substances released therefrom.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention uses MXene and silk fibroin as raw materials, and utilizes the electrostatic spinning technology to easily manufacture the wearable, breathable, degradable, highly sensitive and full-fiber pressure sensor.
The invention aims to provide a sensor based on an MXene/silk fibroin composite material, which comprises an MXene/silk fibroin composite material sensing layer and an MXene three-fork electrode. Wherein the MXene/silk fibroin composite material sensing layer comprises a single layer MXene and silk fibroin; the MXene three-fork electrode comprises a plurality of layers of MXene and silk fibroin; the silk fibroin is selected from silk fibroin fiber membranes.
Another object of the present invention is to provide a method for manufacturing the sensor based on the MXene/silk fibroin composite material, comprising: and respectively preparing an MXene/silk fibroin composite material sensing layer and an MXene interdigital electrode by adopting MXene and silk fibroin, connecting the MXene/silk fibroin film sensing layer and the MXene interdigital electrode together, and inserting a lead wire to obtain the sensor based on the MXene/silk fibroin composite material. The method specifically comprises the following steps:
adding water into an MXene material, and mixing to obtain a homogeneous MXene deposition ink;
printing the MXene deposition ink obtained in the first step on silk fibroin to obtain an MXene interdigital electrode;
step three, spraying an MXene solution on the silk fibroin to obtain an MXene/silk fibroin composite material sensing layer;
and step four, connecting the MXene/silk fibroin composite material sensing layer obtained in the step three with the MXene interdigital electrode obtained in the step two, and then inserting a lead wire to obtain the MXene-based sensor.
In the first step of the preparation method, the MXene material is selected from a plurality of layers of MXene materials; the use ratio of the MXene material to the water is 1:2-1:8, preferably 1:3-1:5, and the MXene deposition ink is prepared by adopting a plurality of layers of MXene materials in the first step, because the MXene deposition ink with larger concentration can be obtained by the plurality of layers of MXene materials, and the single layer MXene is easy to agglomerate in a certain concentration range;
in the first step of the preparation method, the MXene material needs to be ground after being added with water, common grinding equipment (such as a three-roller mill) can be adopted, and the uniform precipitated ink is obtained after grinding. The mixing and grinding operation in the first step is performed at normal temperature.
In the second step of the preparation method, a common screen printer can be used for screen printing the MXene deposition ink on the treated silk fibroin nanofiber membrane to prepare the MXene interdigital electrode. The interdigital electrode obtained by the method improves the contact area, and the resistance of the sensor can be changed drastically by the change amount of the contact area so as to improve the sensitivity of the pressure sensor.
In the third step of the preparation method, the MXene material is selected from a monolithic layer MXene material; the concentration of the MXene solution is 0.1-4 mg/mL, preferably 0.5-1.0 mg/mL; the thickness of the sensing layer of the obtained MXene/silk fibroin composite material is 40-150 mu m, preferably 60-100 mu m; the resistance of the obtained MXene/silk fibroin composite material sensing layer is 1-5000 kΩ, preferably 15-3000 kΩ. In the third step, the sensing layer is prepared by adopting the monolithic layer MXene, because the MXene of the monolithic layer can reduce the resistance of the conductive layer and improve the sensitivity due to high conductivity, and meanwhile, the adhesive force between the monolithic layer and the polymer substrate can be greatly improved due to high specific surface area, so that excellent cycling stability is realized.
The preparation method comprises the steps of adding lithium fluoride into inorganic acid, stirring uniformly, adding titanium aluminum carbon, stirring to obtain an acidic solution, heating for reaction, washing, drying, dissolving the dried multi-layer MXene in water, introducing inert gas, bubbling, performing ultrasonic treatment, centrifuging, and taking upper liquid to obtain a single-layer MXene solution.
In the preparation method of the MXene, the mass ratio of lithium fluoride, inorganic acid and titanium aluminum carbon is 1: (5-8): 1, a step of; adding an inorganic acid selected from hydrofluoric acid; the heating reaction condition is 30-40 ℃ for 3-24 h; the washing condition is that deionized water is used for washing until the pH value of the solution is 6-7; the drying condition after washing is that the freeze drying is carried out for 36 to 48 hours at the temperature of minus 60 ℃ to minus 20 ℃; the water in the MXene solution is deionized water; the ultrasonic treatment time is 30-120 min.
The sensor provided by the invention adopts the excellent characteristics of excellent biocompatibility, biodegradability and the like of the Silk Fibroin (SF), the silk fibroin fiber film with good air permeability is prepared by using an electrostatic spinning process, the pressure sensor prepared by using the silk fibroin fiber film solves the problems that the traditional pressure sensor cannot be worn for a long time and is easy to damage human skin, and meanwhile, the flexible electronic device prepared by using the silk fibroin fiber film with biodegradability has good environmental sustainability and is green and environment-friendly.
The silk fibroin fiber membrane is prepared by degumming silk and adopting an electrostatic spinning technology, and specifically comprises the steps of degumming silk in an alkaline solution, washing, drying, dissolving in a lithium bromide solution, dialyzing the solution in water by using a dialysis bag, centrifuging the obtained silk fibroin solution, freeze-drying, dissolving in an acidic solution, preparing a membrane by adopting the electrostatic spinning technology, drying, and treating by adopting an organic solvent to obtain the silk fibroin fiber membrane. In the preparation process of the silk fibroin fiber film, firstly, a silk fibroin solution is prepared by an alkali degumming method, a silk fibroin nanofiber film is prepared by adopting an electrostatic spinning technology, and then the Silk Fibroin (SF) nanofiber film is treated by an organic solvent to realize water insolubility.
In the preparation method of the silk fibroin fiber membrane, the alkaline solution is at least one selected from sodium bicarbonate solution and sodium carbonate; the concentration of the alkaline solution is 0.01-0.05 mol/L; the concentration of the lithium bromide solution is 5-10 mol/L; the molecular weight cut-off of the dialysis bag is 3000-4000 Da; the dialysis treatment time is 3-7 days; the freeze-drying treatment condition is-20 to-70 ℃ for 12 to 48 hours; the acidic solution is selected from formic acid solution; the mass percentage concentration of the acid solution is 0.5-10%; the drying condition is 20-60 ℃ for 24-36 h; the organic solvent is at least one selected from ethanol, methanol and isopropanol.
It is still another object of the present invention that the MXene/silk fibroin composite material-based sensor described above or the MXene/silk fibroin composite material-based sensor obtained by the above-described preparation method can be applied to, but not limited to, the fields of intelligent electronic skin, human motion detection, clinical diagnosis, and human-computer interaction.
The pressure sensor based on the MXene/silk fibroin composite material is assembled by taking a single-layer MXene sprayed biodegradable silk fibroin nanofiber membrane as a sensing layer and taking a MXene interdigital electrode patterned silk fibroin nanofiber membrane as an electrode layer. Compared with the common sensor with the three-layer structure in the prior art, the sensor with the double-layer structure has better air permeability, and the two-layer structure can fully reduce the loss of force in transmission, improve the sensitivity of the pressure sensor and reduce the response time.
The preparation method of the MXene/silk fibroin composite material sensor is simple in process, and meanwhile, the used natural material is environment-friendly, degradable and good in biocompatibility, and meets the requirements of green chemistry. The MXene/silk fibroin composite material sensor prepared by the method utilizes the excellent conductive performance of MXene to design an MXene interdigital electrode, improves the sensing performance of the sensor, and ensures that the assembled pressure sensor has the excellent performances of wide sensing range, high sensitivity, quick response time and the like. When the pressure is increased, the conductive MXene/silk fibroin nanofiber can effectively increase the contact area of the conductive channel and the interdigital electrode, so that the sensing performance of the sensor is improved, the sensor can be used for ultrasensitive pressure sensing and motion positioning, and has great application prospects in the fields of intelligent electronic skin, human motion detection, clinical diagnosis and human-computer interaction.
Compared with the prior art, the MXene/silk fibroin composite material sensor provided by the invention has the following advantages:
1. the MXene/silk fibroin composite material sensor provided by the invention adopts natural materials as raw materials, has good flexibility, is degradable, is environment-friendly and has good biocompatibility;
2. the sensor provided by the invention is a double-layer structure sensor, has better air permeability, and the double-layer structure can fully reduce the loss of force in transmission, improve the sensitivity of the pressure sensor and reduce the response time;
3. the preparation method provided by the invention has the advantages of simple process, low energy consumption, low cost, environment friendliness, suitability for industrial production and good application prospect.
Drawings
FIG. 1 is an SEM image of an MXene two-dimensional material used in the present invention.
FIG. 2 is an SEM image of a silk fibroin fibrous membrane produced in example 1 of the present invention.
FIG. 3 is a graph showing the air permeability of the silk fibroin fibrous membrane of example 2 of the present invention, wherein a is the air permeability curve of the open system, and b is the air permeability curve of the silk fibroin fibrous membrane of example 2 of the present invention. As can be seen from the air permeability chart of FIG. 3, when the silk fibroin fiber membrane is covered on the water container, the water content of the container covered with the silk fibroin fiber membrane is rapidly reduced along with the time, and the container is close to an open system, so that the silk fibroin fiber membrane prepared by the invention has good air permeability.
FIG. 4 is a graph showing the pressure-current correspondence of pressure sensors assembled with MXene/silk fibroin fiber film sensing layers of different resistances prepared in examples 1 to 5 of the present invention, wherein a to e are the pressure-current curves of the MXene/silk fibroin fiber film sensors prepared in examples 1 to 5, respectively. As can be seen from fig. 4, the sensor is in contact with the sensing layer under the action of pressure, so that a path is realized, the smaller the resistance of the sensing layer is, the larger the change amount of current is, the higher the slope of the obtained curve is, which indicates that the higher the sensitivity of the corresponding sensor is, the smallest the resistance of the sensing layer obtained in embodiment 1 is, and the sensitivity of the corresponding sensor is the highest.
FIG. 5 is a graph of the pressure sensitive performance response of the MXene/silk fibroin-based sensor prepared in example 1 over different pressure ranges, with uniform response at both small (0.36 kPa) and large (39.3 kPa) pressures, demonstrating that the sensor prepared in this regard has a broad response range and stable signal output.
FIG. 6 shows the sensitivity of the MXene/silk fibroin-based sensor prepared in example 1 at various pressures, as can be seen from FIG. 6, the pressure sensor of the present invention realizes good pressure sensitivity (39.3 Kpa) at small pressures (0.36-1.1 kPa) -1 ) Excellent pressure sensitivity (298.4 Kpa) is achieved at a large pressure (1.4 to 16 kPa) -1 ) As the pressure increases further (18-40 kPa), the pressure sensitivity decreases, and the sensor still achieves high sensitivity (171.9 KPa -1 ) The pressure sensor prepared by the invention has wide detection range and high sensitivity characteristic, and the MXene/silk fibroin pressure sensor prepared by the invention has excellent sensitivity no matter small stress or large stress.
FIG. 7 shows the results of sensitivity test data for the MXene/silk fibroin pressure sensor obtained in example 1 and the sensors of comparative examples 1-3, wherein A is the highest sensitivity value for the sensor obtained in example 1 of the present invention, and B-D are the highest sensitivity values for the sensors prepared in comparative examples 1-3, in order.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Test instrument used in the examples:
| instrument name | Device model | Manufacturer' s |
| Desk type high-speed centrifugal machine | MG-1650M | Meier instruments (Shanghai Co., ltd.) |
| Centrifugal machine | HC-3018 | ANHUI USTC ZONKIA SCIENTIFIC INSTRUMENTS Co.,Ltd. |
| Electronic analytical balance | ME204 | Mettler Toledo instruments (Shanghai) Co.,Ltd. |
| Baking oven | DHG-9035A | Shanghai-Hengsu scientific instruments Co., ltd |
| Vertical freeze drier | LGJ-12 | BEIJING SONGYUAN HUAXING TECHNOLOGY DEVELOP Co.,Ltd. |
| Vacuum drying oven | DZF-6020 | Shanghai-Hengsu scientific instruments Co., ltd |
| Magnetic stirrer | ZNCL-GS | HENAN AIBOTE TECHNOLOGY DEVELOPMENT Co.,Ltd. |
| Electrochemical workstation | CHI660E | Shanghai morning Hua Co Ltd |
| Scanning electron microscope | S-4800 | Japanese Hitachi Co Ltd |
| Vertical force measuring machine | ESM303 | Mark-10 Co., ltd |
The test methods used in the examples are as follows:
method for testing air permeability of silk fibroin
The modified silk fibroin film is covered on a 5mL glass sample bottle containing 1g of water and having the caliber of 10mm, an open small bottle is arranged as a blank group, and the study of the air permeability of different films is realized by periodically measuring the residual amount of water in the small bottle under the same environment.
Method for testing pressure-sensitive performance
Connecting the prepared pressure sensor with an electrochemical workstation through a copper wire, placing the pressure sensor on a mechanical tester platform, setting different pressures to obtain a corresponding relation diagram of the pressure and the current, and processing dataObtaining delta I/I 0 The ratio to pressure gives the pressure sensor sensitivity S. The pressure sensor sensitivity (S) is expressed as the ratio of the electrical output to the normalized change in applied strain, and the sensitivity coefficient is a parameter indicative of the sensor sensitivity and is the slope of the sensing curve (sensitivity graph) expressed as s=δ (Δi/I) 0 )/δP。
The raw materials and sources used in the examples are as follows:
| material name | Purity of | Manufacturer(s) |
| Silkworm cocoon | Commercially available | |
| Lithium fluoride | AR | Alfa Aesar |
| Hydrochloric acid | AR | BEIJING CHEMICAL PLANT |
| Sodium bicarbonate | AR | BEIJING CHEMICAL PLANT |
| Ethanol | AR | BEIJING CHEMICAL PLANT |
| Lithium bromide | AR | Shanghai Miclin technologies Co.Ltd |
| Formic acid | AR | BEIJING CHEMICAL PLANT |
| Ti3AlC2 MAX phase | 500 mesh | One of the science and technology Co Ltd |
| Dialysis bag | Siderurgica Ruisi (Beijing) technology Co., ltd |
Example 1:
preparation of MXene material:
firstly, preparing a plurality of layers of MXene: a9 mol/mL hydrochloric acid (HCl) solution was prepared, and 20mL of the hydrochloric acid solution was measured and poured into a polytetrafluoroethylene beaker, and then 1g of lithium fluoride (LiF) was weighed and placed into the polytetrafluoroethylene beaker, and the mixed solution was uniformly mixed and stirred at room temperature by a magnetic stirrer. Subsequently 1g of Ti 3 AlC 2 The raw materials are slowly added into a polytetrafluoroethylene beaker and stirred uniformly, so that local overheating caused by exothermic reaction is avoided. The reaction was then placed in a 35 ℃ oil bath magnetic stirrer for 24h. Pouring the reacted solution into a centrifuge tube, centrifuging for 5min at 3500rpm, taking the lower precipitate, repeatedly washing with deionized water until the pH of the supernatant is about 6, centrifuging to obtain a precipitate which is multi-lamellar MXene, and drying the obtained multi-lamellar MXene in a freeze dryer at-60 ℃ for 36h to obtain powder multi-lamellar MXene.
FreezingThe dried multi-layered MXene was dissolved in deionized water and argon was introduced to exclude oxygen and subjected to bubbling sonication for 40min. Pouring the ultrasonic dispersion into a centrifuge tube and centrifuging at 3500rpm for 1h to obtain uniform layered Ti 3 C 2 T X Obtaining the single-layer MXene solution by supernatant.
Preparing a silk fibroin nanofiber membrane:
firstly, preparing silk fibroin spinning solution, firstly, preparing silkworm cocoons into 0.02M NaHCO 3 Boiling in water solution for 30min, repeating for 3 times to achieve degumming, washing with deionized water to remove colloidal sericin and wax, and drying degummed silk fiber in oven at 60deg.C for 24 hr. The extracted silk fibers were then dissolved in 9.3M LiBr solution and the solution was dialyzed against deionized water using a dialysis bag (3500 Da molecular weight cutoff) for 3 days. Then, the obtained silk fibroin solution was centrifuged at 3000rpm for 30min and frozen at-20 ℃ for 12h to obtain a regenerated silk fibroin sponge, which was then dissolved in formic acid solution (1.5 wt%) to form a spinning solution.
And (3) adopting an electrostatic spinning technology to prepare a film from the prepared spinning solution, wherein the flow rate of the solution is 1mL/h, and the electric strength is 1kV/cm. For safety, the electrospun samples were sealed and dried in a fume hood to remove harmful gases. Finally, the silk fibroin nanofiber membrane was post-treated with ethanol of different concentrations (50-100 wt%) for 30min to achieve water insolubility.
Preparation of a sensor based on an MXene/silk fibroin composite:
step one: preparation of MXene deposition ink: using the above-described preparation of multi-lamellar MXene, adding deionized water to obtain a 20wt% multi-lamellar solution, and treating by three-roll milling to form a homogeneous precipitated ink;
step two: screen printing an MXene deposition ink onto the silk fibroin fibrous membrane prepared above using a commercially available screen printer to form an MXene interdigital electrode;
step three: spraying a single-layer MXene solution with the concentration of 0.5mg/mL on a silk fibroin fiber membrane to construct a sensing layer, and regulating the sprayed MXene to obtain a conductive MXene/silk fibroin membrane sensing layer with the resistance of 15kΩ and the thickness of 60 mu m;
step four: and (3) connecting the conductive MXene/silk fibroin film sensing layer obtained in the step (III) and the conductive MXene interdigital electrode obtained in the step (II) together in a face-to-face manner, and leading out the conductive MXene/silk fibroin film sensing layer from the interdigital electrode by using two copper wires to obtain the sensor based on the MXene/silk fibroin composite material.
The sensor based on the MXene/silk fibroin composite material is communicated with an external circuit, and can be placed on a test bench to perform pressure-sensitive performance test.
Example 2:
the MXene material and silk fibroin nanofiber membrane prepared in example 1 were used.
Preparation of a sensor based on an MXene/silk fibroin composite:
firstly, preparing MXene deposition ink, adding deionized water into the prepared multi-layer MXene to obtain a multi-layer solution with the weight percent of 20%, and performing three-roll grinding treatment to form homogeneous precipitation ink;
step two, screen printing MXene deposition ink to the prepared silk fibroin fiber membrane by using a commercially available screen printer to form an MXene interdigital electrode;
step three, spraying a single-layer MXene solution with the concentration of 1mg/mL on a silk fibroin fiber membrane to construct a sensing layer, and regulating the sprayed MXene to obtain a conductive MXene/silk fibroin membrane sensing layer with the resistance of 60kΩ and the thickness of 60 mu m;
and fourthly, connecting the conductive MXene/silk fibroin film sensing layer obtained in the third step with the conductive MXene interdigital electrode obtained in the second step face to face, and leading out the conductive MXene/silk fibroin film sensing layer from the interdigital electrode by using two copper wires to obtain the sensor based on the MXene/silk fibroin composite material.
The sensor based on the MXene/silk fibroin composite material is communicated with an external circuit, and can be placed on a test bench to perform pressure-sensitive performance test.
Example 3:
the MXene material and silk fibroin nanofiber membrane prepared in example 1 were used.
Preparation of a sensor based on an MXene/silk fibroin composite:
step one, preparing MXene deposition ink, namely preparing multi-layer MXene by using the method, adding deionized water to obtain a multi-layer solution with the weight percent of 20%, and performing three-roll grinding treatment to form homogeneous precipitation ink;
step two, screen printing MXene deposition ink to the prepared silk fibroin fiber membrane by using a commercially available screen printer to form an MXene interdigital electrode;
step three, spraying a single-layer MXene solution with the concentration of 1.5mg/mL on a silk fibroin fiber membrane to construct a sensing layer, and regulating the sprayed MXene to obtain a conductive MXene/silk fibroin membrane sensing layer with the resistance of 650kΩ and the thickness of 80 mu m;
and fourthly, connecting the conductive MXene/silk fibroin film sensing layer obtained in the third step with the conductive MXene interdigital electrode obtained in the second step in a face-to-face manner, and leading out the conductive MXene/silk fibroin film sensing layer from the interdigital electrode by using two copper wires to obtain the sensor based on the MXene/silk fibroin composite material.
The sensor based on the MXene/silk fibroin composite material is communicated with an external circuit, and can be placed on a test bench to perform pressure-sensitive performance test.
Example 4:
the MXene material and silk fibroin nanofiber membrane prepared in example 1 were used.
Preparation of a sensor based on an MXene/silk fibroin composite:
preparing MXene deposition ink, namely preparing multi-layer MXene by using the method, adding deionized water to obtain a multi-layer solution with the weight percent of 20%, and performing three-roll grinding treatment to form homogeneous precipitation ink;
step two, screen printing MXene deposition ink to the prepared silk fibroin fiber membrane by using a commercially available screen printer to form an MXene interdigital electrode;
step three, spraying a single-layer MXene solution with the concentration of 2mg/mL on a silk fibroin fiber membrane to construct a sensing layer, and regulating the sprayed MXene to obtain a conductive MXene/silk fibroin membrane sensing layer with the resistance of 1600kΩ and the thickness of 80 mu m;
and fourthly, connecting the conductive MXene/silk fibroin film sensing layer obtained in the third step with the conductive MXene interdigital electrode obtained in the second step face to face, and leading out the conductive MXene/silk fibroin film sensing layer from the interdigital electrode by using two copper wires to obtain the sensor based on the MXene/silk fibroin composite material.
The sensor based on the MXene/silk fibroin composite material is communicated with an external circuit, and can be placed on a test bench to perform pressure-sensitive performance test.
Example 5:
the MXene material and silk fibroin nanofiber membrane prepared in example 1 were used.
Preparation of a sensor based on an MXene/silk fibroin composite:
step one, preparing MXene deposition ink: using the multi-lamellar MXene prepared above, adding deionized water to obtain a 20wt% multi-lamellar solution, and treating by three-roll milling to form a homogeneous precipitated ink;
step two, screen printing MXene deposition ink to the prepared silk fibroin fiber membrane by using a commercially available screen printer to form an MXene interdigital electrode;
step three, spraying a monolithic layer MXene solution with the concentration of 3mg/mL on a silk fibroin fiber membrane to construct a sensing layer, and regulating the sprayed MXene to obtain a conductive MXene/silk fibroin membrane sensing layer with the resistance of 3000kΩ and the thickness of 100 mu m;
and fourthly, connecting the conductive MXene/silk fibroin film obtained in the third step and the conductive MXene interdigital electrode obtained in the second step together in a face-to-face manner, and leading out the conductive MXene/silk fibroin film from the interdigital electrode by using two copper wires to obtain the sensor based on the MXene/silk fibroin composite material.
The sensor based on the MXene/silk fibroin composite material is communicated with an external circuit, and can be placed on a test bench to perform pressure-sensitive performance test.
Comparative example 1
Using literature (Z.Y. zhang, et al paper/carbon nanotube-BasedWearable Pressure Sensor for Physiological Signal Acquisition and Soft Robotic Skin [ J)].ACS Applied Materials&Interfaces,2017,9(43):37921-37928. ) The sensor prepared by thin paper, polydimethylsiloxane and polyimide soaked with single-wall carbon nano-tubes has the disclosed pressure-sensitive test result that the widest detection range is 11.7kPa and the highest detection sensitivity is 2.2kPa -1 (see B in fig. 7). As can be seen from FIG. 7, both of these data for the sensor of comparative example 1 are much lower than the maximum detection sensitivity (298.4 kPa) of the widest detection range (40 kPa) of the sensor of the present invention (see FIG. 7A) -1 ) Meanwhile, the polydimethylsiloxane and polyimide films have no air permeability, and the silk protein film adopted by the invention has good air permeability, and can be completely degradable and meets the requirements of green chemistry.
Comparative example 2
A sensor assembled by adopting natural viscoelastic materials VDF-TrFe combined with reduced graphene oxide and polydimethylsiloxane in literature (K.Jiang, G.Z.Shen, et al, an UltraSensitive and Rapid Response Speed Graphene Pressure Sensors for Electronic Skin and Health monitoring. Nano Energy 2016,23,7-14.) has the disclosed pressure-sensitive test experimental result that the widest detection range is 60kPa and the highest detection sensitivity is 15.6kPa -1 (see C in FIG. 7), although the widest detection range is higher than that of the present invention (40 kPa), the highest detection sensitivity is far lower than that of the sensor of the present invention (298.4 kPa-1) (see A in FIG. 7), while the polydimethylsiloxane has no air permeability, and the fibroin film used in the present invention has good air permeability, while achieving complete degradability in accordance with the requirements of green chemistry.
Comparative example 3
A sensor prepared from poly (3, 4-ethylenedioxythiophene monomer: styrene sulfonate) (PEDOT: PSS)) and an aqueous Polyurethane (PUD) elastomer mixture, polydimethylsiloxane in literature (C. -L.choong, et al high Stretchable Resistive Pressure Sensors Using a Conductive Elastomeric Composite on a Micropyramid array. Adv. Mater.2014,26, 3451-3458.) was disclosed with a pressure sensitive test experiment with a widest detection range of 10kPa and a highest detection sensitivity of 4.88kPa -1 (see D in FIG. 7), both of these data for the sensor of comparative example 3 are much lower thanThe maximum detection sensitivity (298.4 kPa) of the widest detection range (40 kPa) of the sensor of the present invention -1 ) (see A in FIG. 7), while the polydimethylsiloxane has no air permeability, the fibroin film adopted by the invention has good air permeability, and can be completely degradable and meets the requirements of green chemistry.
Therefore, the sensor based on the MXene/silk fibroin composite material provided by the invention has better air permeability, and the double-layer structure can sufficiently reduce the loss of force in transmission and improve the sensitivity of the pressure sensor.
Claims (9)
1. A sensor based on an MXene/silk fibroin composite material comprises an MXene/silk fibroin composite material sensing layer and an MXene three-fork electrode, wherein the sensor is a pressure sensor;
the MXene/silk fibroin composite material sensing layer comprises a single layer MXene and silk fibroin, and the single layer MXene solution is sprayed on the silk fibroin to obtain the MXene/silk fibroin composite material sensing layer;
the MXene three-fork electrode comprises a plurality of layers of MXene and silk fibroin, and the MXene three-fork electrode is obtained by printing a plurality of layers of MXene deposition ink on the silk fibroin;
the silk fibroin is selected from silk fibroin fiber membranes.
2. A method of manufacturing an MXene/silk fibroin composite based sensor according to claim 1, comprising the steps of:
adding water into an MXene material, and mixing to obtain a homogeneous MXene deposition ink;
printing the MXene deposition ink obtained in the first step on silk fibroin to obtain an MXene interdigital electrode;
step three, spraying an MXene solution on the silk fibroin to obtain an MXene/silk fibroin composite material sensing layer;
and step four, connecting the MXene/silk fibroin composite material sensing layer obtained in the step three with the MXene interdigital electrode obtained in the step two, and then inserting a lead wire to obtain the MXene-based sensor.
3. The method according to claim 2, wherein,
the MXene material in the first step is a multi-layer MXene material; and/or the number of the groups of groups,
the dosage ratio of the MXene material to the water in the first step is 1:2-1:8; and/or the number of the groups of groups,
the MXene material in the first step needs grinding treatment after being added with water; and/or the number of the groups of groups,
the MXene material in the third step is a monolithic layer MXene material; and/or the number of the groups of groups,
the concentration of the MXene solution in the third step is 0.1-4 mg/mL; and/or the number of the groups of groups,
the thickness of the sensing layer of the MXene/silk fibroin composite material is 40-150 mu m; and/or the number of the groups of groups,
the resistance of the MXene/silk fibroin composite material sensing layer obtained in the third step is 1-5000 kΩ; and/or the number of the groups of groups,
the silk fibroin in the second step or the third step is silk fibroin fiber membrane.
4. A process according to claim 3, wherein,
the dosage ratio of the MXene material to the water in the first step is 1:3-1:5; and/or the number of the groups of groups,
the concentration of the MXene solution in the third step is 0.5-1.0 mg/mL; and/or the number of the groups of groups,
the thickness of the sensing layer of the MXene/silk fibroin composite material is 60-100 mu m; and/or the number of the groups of groups,
and (3) the resistance of the MXene/silk fibroin composite material sensing layer obtained in the step (III) is 15-3000 kΩ.
5. The preparation method of the single-layer MXene solution is characterized in that MXene is obtained by etching titanium aluminum carbon through hydrofluoric acid, and the preparation method specifically comprises the steps of adding lithium fluoride into inorganic acid, stirring uniformly, adding titanium aluminum carbon, stirring to obtain an acidic solution, heating for reaction, washing, drying, dissolving a plurality of dried layers of MXene in water, introducing inert gas, bubbling, conducting ultrasonic treatment, centrifuging, and taking upper liquid to obtain the single-layer MXene solution.
6. The method according to claim 5, wherein,
the mass ratio of the lithium fluoride to the inorganic acid to the titanium aluminum carbon is 1: (5-8): 1, a step of; and/or the number of the groups of groups,
the inorganic acid is selected from hydrofluoric acid; and/or the number of the groups of groups,
the heating reaction condition is 30-40 ℃ for 3-24 hours; and/or the number of the groups of groups,
the washing condition is that deionized water is used for washing until the pH value of the solution is 6-7; and/or the number of the groups of groups,
the drying is freeze drying at the temperature of minus 60 ℃ to minus 20 ℃; and/or the number of the groups of groups,
the drying time is 36-48 h; and/or the number of the groups of groups,
the water is deionized water; and/or the number of the groups of groups,
the ultrasonic treatment time is 30-120 min.
7. The preparation method of the silk fibroin fiber membrane according to claim 2, wherein the silk fibroin fiber membrane is prepared by degumming silk and adopting an electrostatic spinning technology, the specific preparation method comprises the steps of degumming silk in an alkaline solution, washing, drying, dissolving in a lithium bromide solution, dialyzing the solution in water by using a dialysis bag, centrifuging the obtained silk fibroin solution, freeze-drying, dissolving in an acid solution, preparing a membrane by adopting the electrostatic spinning technology, drying, and treating by adopting an organic solvent, thus obtaining the silk fibroin fiber membrane.
8. The method according to claim 7, wherein,
the alkaline solution is at least one selected from sodium bicarbonate solution and sodium carbonate; and/or the number of the groups of groups,
the concentration of the alkaline solution is 0.01-0.05 mol/L; and/or the number of the groups of groups,
the concentration of the lithium bromide solution is 5-10 mol/L; and/or the number of the groups of groups,
the molecular weight cut-off of the dialysis bag is 3000-4000 Da; and/or the number of the groups of groups,
the dialysis treatment time is 3-7 days; and/or the number of the groups of groups,
the freeze-drying treatment conditions are-20 to-70 ℃ and 12 to 48 hours; and/or the number of the groups of groups,
the acid solution is selected from formic acid solution; and/or the number of the groups of groups,
the mass percentage concentration of the acid solution is 0.5-10%; and/or the number of the groups of groups,
the drying condition is 20-60 ℃ for 24-36 hours; and/or the number of the groups of groups,
the organic solvent is at least one selected from ethanol, methanol and isopropanol.
9. Use of a sensor based on an MXene/silk fibroin composite according to claim 1 or obtained by the preparation method according to any of claims 2 to 8, characterized in that said sensor is applied in the fields of intelligent electronic skin, human motion detection, clinical diagnostics and human-computer interaction.
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