CN116355462A - Conductive ink without polymer matrix, composite sensor and preparation method thereof - Google Patents
Conductive ink without polymer matrix, composite sensor and preparation method thereof Download PDFInfo
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- CN116355462A CN116355462A CN202310357575.8A CN202310357575A CN116355462A CN 116355462 A CN116355462 A CN 116355462A CN 202310357575 A CN202310357575 A CN 202310357575A CN 116355462 A CN116355462 A CN 116355462A
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
Abstract
The invention discloses a conductive ink without a polymer matrix, a composite sensor and a preparation method thereof, wherein the conductive ink comprises a solvent, and reduced graphene oxide and MXene which are dispersed in the solvent and are connected through a Ti-O-C covalent bond. The conductive ink provided by the invention adopts the synergistic combination of the reduced graphene oxide and the MXene, does not contain an additional polymer matrix, and establishes a non-invasive condition for embedding the sensor in the main prepreg composite material. The embedded sensor prepared from the conductive ink can be fully impregnated by the main prepreg composite material, so that the thermal behavior mismatch between the sensor and the main prepreg composite material is prevented, the cracking and the structural deterioration caused by the temperature change during the use due to the difference of the thermal expansion coefficients are avoided, the mechanical property and the structural integrity of the main prepreg composite material are reserved, and the mechanical property of the main prepreg composite material is not influenced by the integration of the sensor.
Description
Technical Field
The invention relates to the technical field of functional ink, in particular to conductive ink without a polymer matrix, a composite sensor and a preparation method thereof.
Background
Conductive ink is an important material for manufacturing functional layers, and the functional layers can be used as sensors in the fields of intelligent electronics, medical care, aerospace and the like. The existing conductive ink generally comprises a conductive filler and a polymer matrix, and when the sensor prepared from the conductive ink is integrated into a main prepreg composite material to prepare the intelligent composite material, the difference of the sensor and the polymer in the main prepreg composite material can cause mismatch of thermal behaviors of the sensor and the main prepreg composite material, delamination, cracking and structural deterioration can be caused along with temperature change during use due to difference of thermal expansion coefficients, the overall mechanical property of the main prepreg composite material is reduced, and delamination and cracks around a sensor area can also reduce the sensing performance of the sensor, even the sensor can lose sensing capability. Thus, a major challenge in developing a sensor that matches the primary prepreg composite is the conductive ink formulation.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a conductive ink without a polymer matrix, a composite sensor and a preparation method thereof, and aims to solve the problem that the thermal behavior of a sensor prepared by the conventional conductive ink is not matched with that of a main prepreg composite material, so that the overall mechanical property of the main prepreg composite material is reduced.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a polymer matrix-free conductive ink comprising a solvent, and reduced graphene oxide and MXene dispersed in the solvent, the reduced graphene oxide and MXene being connected by a Ti-O-C covalent bond.
Optionally, the solvent is a polar solvent, and the polar solvent includes at least one of water, ethanol, isopropanol, dimethylformamide, and N-methylpyrrolidone.
In a second aspect of the present invention, there is provided a method for preparing the polymer matrix-free conductive ink according to the present invention, comprising the steps of:
providing a graphene oxide dispersion and an MXene dispersion, the solvent of the graphene oxide dispersion and the MXene dispersion comprising at least water;
mixing the graphene oxide dispersion liquid and the MXene dispersion liquid to obtain a composite dispersion liquid;
adding a reducing agent into the composite dispersion liquid to perform a reduction reaction to obtain hydrogel containing reduced graphene oxide and MXene; or, adding a reducing agent and an alkaline substance into the composite dispersion liquid to perform a reduction reaction to obtain hydrogel containing reduced graphene oxide and MXene;
washing the hydrogel until the pH value of the hydrogel is neutral;
dispersing the washed hydrogel in a solvent to obtain the conductive ink without the polymer matrix.
Optionally, the reducing agent comprises at least one of ascorbic acid, cysteine, hydrazine hydrate, dimethylhydrazine, sodium citrate, hydrogenated acetic acid, sodium borohydride, hydrohalic acid, fuming sulfuric acid.
Optionally, the alkaline substance includes at least one of sodium hydroxide and potassium hydroxide.
Alternatively, the temperature of the reduction reaction is 60-95 ℃, and the time of the reduction reaction is 6-12 hours.
Optionally, the MXene comprises Ti 3 C 2 、Ti 2 C、Ti 3 At least one of the CNs.
In a third aspect of the invention, a composite sensor is provided, wherein the composite sensor comprises a prepreg layer, a sensor body embedded in the prepreg layer and a conductive wire connected with the sensor body, and the sensor body comprises reduced graphene oxide and MXene connected with the reduced graphene oxide through a Ti-O-C covalent bond.
Optionally, the conductive wire comprises at least one of a metal wire, a carbon nanotube fiber wire, and a carbon fiber wire;
the prepreg comprises one of glass fiber prepreg, aramid fiber prepreg, carbon fiber prepreg and natural fiber-based prepreg.
According to a fourth aspect of the present invention, there is provided a method for manufacturing the composite sensor according to the present invention, comprising the steps of:
providing a prepreg layer;
dropping the conductive ink without the polymer matrix on the prepreg layer or dropping the conductive ink without the polymer matrix prepared by the preparation method on the prepreg layer, and drying to form a sensor body;
a conductive wire is arranged on the sensor body;
and forming a prepreg layer on the sensor body and the conductive wire, and drying and curing to obtain the composite sensor.
The beneficial effects are that: the conductive ink provided by the invention adopts the synergistic combination of the reduced graphene oxide and the MXene, does not contain an additional polymer matrix, establishes a non-invasive condition for embedding the sensor in the main prepreg composite material to manufacture the intelligent composite material, and enables the sensor to be embedded in the main prepreg composite material under a non-invasive condition. The embedded sensor prepared from the conductive ink can be completely impregnated by the main prepreg composite material, so that the thermal behavior mismatch between the sensor and the main prepreg composite material is prevented, the cracking and the structural deterioration caused by the temperature change during the use due to the difference of the thermal expansion coefficients are avoided, the mechanical properties (such as mechanical properties) and the structural integrity of the main prepreg composite material are reserved, and the mechanical properties of the main prepreg composite material are not influenced by the integration of the sensor. Meanwhile, the combination effect of the reduced graphene oxide and the MXene synergistically improves the use path of the sensor.
Drawings
FIG. 1 is a topography of a composite sensor according to example 2 of the present invention.
FIG. 2 is a graph showing the results of average interlaminar shear strength of the composite sensor of example 2 and the composite material of comparative example 1 according to the present invention.
FIG. 3 is a graph showing the sensitivity test results of the composite sensor according to example 2 of the present invention.
Detailed Description
The invention provides a conductive ink without a polymer matrix, a composite sensor and a preparation method thereof, and aims to make the purposes, the technical scheme and the effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The prepreg is a composition of a resin matrix and a reinforcement made by impregnating continuous fibers or fabrics with the resin matrix under tightly controlled conditions. The prepreg, the primary prepreg composite, have the same meaning herein.
While the existing conductive ink generally comprises a conductive filler and a polymer matrix, when the sensor prepared by the conductive ink is integrated into the main prepreg composite material to prepare the intelligent composite material, the difference of the sensor and the polymer in the main prepreg composite material can cause mismatch of thermal behaviors of the sensor and the main prepreg composite material, delamination, cracking and structural deterioration can be caused along with temperature change during use due to difference of thermal expansion coefficients, the overall mechanical property of the main prepreg composite material is reduced, and delamination and cracks around a sensor area can also reduce the sensing performance of the sensor, even the sensor can lose sensing capability. Based on the above, the embodiment of the invention provides a conductive ink without a polymer matrix, which comprises a solvent, and reduced graphene oxide and MXene dispersed in the solvent, wherein the reduced graphene oxide and the MXene are connected through a Ti-O-C covalent bond.
The conductive ink provided by the embodiment of the invention adopts the synergistic combination of the reduced graphene oxide and the MXene, does not contain an additional polymer matrix, establishes a non-invasive condition for embedding the sensor in the main prepreg composite material to manufacture the intelligent composite material, and enables the sensor to be embedded in the main prepreg composite material under a noninvasive condition. The embedded sensor prepared from the conductive ink can be completely impregnated by the main prepreg composite material, so that the thermal behavior mismatch between the sensor and the main prepreg composite material is prevented, the cracking and the structural deterioration caused by the temperature change during the use due to the difference of the thermal expansion coefficients (the difference of the expansion coefficients caused by the difference of polymers) are avoided, the mechanical properties (such as mechanical properties) and the structural integrity of the main prepreg composite material are reserved, and the mechanical properties of the main prepreg composite material are not influenced by the integration of the sensor. Meanwhile, the reduced graphene oxide and the MXene are connected through a Ti-O-C covalent bond, and the combination effect of the reduced graphene oxide and the MXene is improved cooperatively, so that the use path of the sensor is improved cooperatively.
In the embodiment of the invention, the content of the reduced graphene oxide and the MXene is not limited, and can be adjusted according to the actual required performance.
MXene is a two-dimensional material composed of surface-modified carbide with high metallic conductivity, its hydrophilicity and high negative surface electrical, allowing it to disperse in polar solvents (e.g., water) to form a stable colloidal solution, in this example, the presence of MXene helps the reduced graphene oxide to disperse uniformly in the solvent, reducing agglomeration.
In some embodiments, the solvent is a polar solvent. In some specific embodiments, the polar solvent includes at least one of water, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone, but is not limited thereto.
The embodiment of the invention also provides a preparation method of the conductive ink without the polymer matrix, which comprises the following steps:
s11, providing a graphene oxide dispersion liquid and an MXene dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid and the MXene dispersion liquid at least comprises water;
s12, mixing the graphene oxide dispersion liquid and the MXene dispersion liquid to obtain a composite dispersion liquid;
s13, adding a reducing agent into the composite dispersion liquid, and performing a reduction reaction to obtain hydrogel containing reduced graphene oxide and MXene; or, adding a reducing agent and an alkaline substance into the composite dispersion liquid to perform a reduction reaction to obtain hydrogel containing reduced graphene oxide and MXene;
s14, cleaning the hydrogel until the pH value of the hydrogel is neutral;
and S15, dispersing the washed hydrogel in a solvent to obtain the conductive ink without the polymer matrix.
Graphene has excellent conductivity and unique physical properties, and is an ideal sensing material for sensors. The graphene-based sensor has high sensitivity, rapid response and durability, and can satisfy various applications. However, due to the strong interplay of van der Waals force and pi-pi between planes of graphene, the graphene is often subjected to aggregation phenomenon, so that the exertion of excellent physical and chemical properties of the graphene is influenced, the sensing performance is poor, in addition, stress concentration can be generated due to aggregation, and the mechanical property of the composite material is deteriorated. In the research started by the invention, graphene oxide containing abundant hydrophilic groups is taken as a raw material, and reduced into reduced graphene oxide to form porous hydrogel, and meanwhile, the properties of the graphene are maintained. The electrostatic repulsive force between the nano sheets in the auxiliary reduction process of the reducing agent is used under the alkaline condition to realize the stability of the colloid, so that the agglomeration of the reduced graphene oxide nano sheets is prevented, and the problem of easy agglomeration of graphene is solved. The porous structure of the hydrogel results from phase separation between the water and the reduced graphene oxide network during the reduction process. Although the porous flexible strain sensor made of the hydrogel containing the reduced graphene oxide has the characteristics of large surface area, low density, good stretchability, quick response and the like, the sensitivity is limited, and the detection in a linear range still has the defects. Therefore, the invention further researches that the MXene and the reduced graphene oxide are compounded to prepare the conductive ink, and the sensitivity of the sensor prepared from the conductive ink can be further improved in a wide linear range while ensuring that the reduced graphene oxide in the conductive ink is not agglomerated by utilizing the hydrophilic characteristic of the MXene, and meanwhile, the quick response, high fatigue resistance and low detection line are ensured. Specifically, a reducing agent (or a reducing agent and an alkaline substance) is added to a dispersion liquid containing graphene oxide and MXene, the graphene oxide is reduced to form a hydrogel containing reduced graphene oxide and MXene, and then the hydrogel is redispersed in a solvent to prepare the conductive ink without a polymer matrix.
In the embodiment of the invention, with the help of the reducing agent, the stacking of graphene oxide and MXene nano-sheets is blocked, and agglomeration is prevented. Meanwhile, the alkaline substance is favorable for improving the colloid stability of graphene oxide and MXene nano-sheets in the reduction process, so that the stability of the prepared conductive ink is ensured. In addition, electrostatic repulsive force between the reduced graphene oxides ensures that the reduced graphene oxides are not agglomerated, and the dispersibility of the reduced graphene oxides is further improved by the existence of MXene.
In addition, the reducing agent is used as a reducing and functional chemical substance, and the bonding of Ti-O-C bonds between the reduced graphene oxide and MXene is realized while the reduced graphene oxide is reduced.
In step S11, the solvent of the graphene oxide dispersion liquid and the MXene dispersion liquid may further include a polar solvent.
In some embodiments, the method of preparing the graphene oxide dispersion comprises the steps of:
adding graphene oxide into water or a polar solvent containing water, and carrying out ultrasonic treatment for 15-60 minutes to obtain the graphene oxide dispersion liquid.
The graphene oxide is prepared from graphite powder serving as a raw material by an improved Hummers method, and the method is the prior art and is not described in detail herein.
In some embodiments, the method of preparing the MXene dispersion comprises the steps of:
adding the MXene into water or a polar solvent containing water, and carrying out ultrasonic treatment for 15-60 minutes to obtain the MXene dispersion liquid.
In some embodiments, the MXene comprises Ti 3 C 2 、Ti 2 C、Ti 3 At least one of CN, but not limited thereto. The MXene can be purchased directly or synthesized by oneself. With Ti 3 C 2 In the case of an example of this,the preparation method of the MXene comprises the following steps:
providing Ti 3 AlC 2 (MAX phase), ti is dissolved by etching solution 3 AlC 2 Etching away the Al atomic layer in the alloy to obtain Ti 3 AlC 2 。
Specifically, the etching liquid comprises one of lithium fluoride solution, hydrochloric acid and hydrofluoric acid.
In step S13, the reducing agent and the alkaline substance may be directly added to the composite dispersion liquid, or the reducing agent and the alkaline substance may be prepared into a solution, and then added to the composite dispersion liquid in the form of a solution, or the composite dispersion liquid may be added to the reducing agent solution and the alkaline substance solution.
In some embodiments, the reducing agent includes at least one of ascorbic acid, cysteine, hydrazine hydrate, dimethylhydrazine, sodium citrate, hydrogenated acetic acid, sodium borohydride, hydrohalic acid, fuming sulfuric acid, but is not limited thereto. Preferably, the reducing agent is ascorbic acid or cysteine. The two reducing agents are adopted, so that the preparation process of the conductive ink is economical, nontoxic and environment-friendly.
In some embodiments, the alkaline substance includes at least one of sodium hydroxide and potassium hydroxide, but is not limited thereto.
In some embodiments, the temperature of the reduction reaction is 60-95 ℃, e.g., 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, or 95 ℃; the reduction reaction time is 6-12 hours, and may be, for example, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.
In step S14, in some embodiments, the hydrogel is washed with at least one of water, ethanol, hydrochloric acid until the pH of the hydrogel is neutral.
In step S15, the step of dispersing the washed hydrogel in a solvent to obtain the conductive ink without a polymer matrix specifically includes:
and adding the cleaned hydrogel into a solvent, stirring for 1-24h, and performing ultrasonic treatment for 1-60min to obtain the conductive ink without the polymer matrix.
In some embodiments, the solvent is a polar solvent. In some specific embodiments, the polar solvent includes at least one of water, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone, but is not limited thereto.
The embodiment of the invention also provides a composite sensor, which comprises a prepreg layer, a sensor body embedded in the prepreg layer and a conductive wire connected with the sensor body, wherein the sensor body comprises reduced graphene oxide and MXene connected with the reduced graphene oxide through a Ti-O-C covalent bond. The conductive wire can penetrate through the prepreg layer and is exposed out of the composite sensor, and is connected with an external device when the composite sensor is applied.
In embodiments of the present invention, the sensor body does not contain an additional polymer matrix, creating non-invasive conditions for embedding the sensor body in the prepreg to make the smart composite, enabling the embedding of the prepreg under non-invasive conditions. Therefore, the problem of thermal behavior mismatch between the sensor body and the prepreg is not generated, and further the prepreg body is not cracked and structurally deteriorated, so that the mechanical properties of the prepreg are not affected by sensor integration, and at the same time, the use of the prepreg can also prevent structural deterioration caused by thermal expansion mismatch, which may be caused at high temperature. The composite sensor provided by the embodiment of the invention maintains the mechanical properties (such as mechanical properties) and structural integrity of the prepreg.
In some embodiments, the conductive wire includes at least one of a metal wire (e.g., copper wire, etc.), a carbon nanotube fiber wire, and a carbon fiber wire, but is not limited thereto.
In some embodiments, the prepreg includes one of glass fiber prepreg, aramid fiber prepreg, carbon fiber prepreg, natural fiber-based prepreg, but is not limited thereto. These prepregs may be unidirectional prepregs or woven prepregs.
In some embodiments, the prepreg layer is a multi-layer structure, and may be disposed according to actual needs. In one example, the prepreg layers include a first prepreg layer and a second prepreg layer, and the sensor is positioned between the first prepreg layer and the second prepreg layer. In further examples, the prepreg layers include a stack of first, second, and third prepreg layers, with the sensor positioned between the second and third prepreg layers. The first, second and third prepregs of the first, second and third prepregs are each independently selected from glass fiber prepregs, aramid fiber prepregs, carbon fiber prepregs or natural fiber-based prepregs, but are not limited thereto.
The embodiment of the invention also provides a preparation method of the composite sensor, which comprises the following steps:
s21, providing a prepreg layer;
s22, dropwise adding the conductive ink without the polymer matrix in the embodiment of the invention on the prepreg layer or dropwise adding the conductive ink without the polymer matrix prepared by the preparation method in the embodiment of the invention on the prepreg layer, and drying to form a sensor body;
s23, arranging a conductive wire on the sensor body;
s24, forming a dipping layer on the sensor body and the conductive wire again, and drying and curing to obtain the sensor.
Existing sensors are typically mounted on the surface of a host structure and are easy to install and maintain, however, they are prone to failure and detachment when exposed to extreme replacement environments, and lack feasibility, resulting in lower sensing performance and accuracy. On the other hand, because the inside of the composite material structure is easy to generate damages such as matrix cracking or layering, the sensor is required to monitor, and the embedded sensor in the composite material structure can improve the signal acquisition precision and the stability of long-term monitoring service. The embedded sensors have a longer life than surface mounted sensors because they are protected from the adverse environment by the host structure. However, due to the too thick thickness of the sensor and the thermal behavior mismatch between the sensor and the host material, improper sensor integration may result in delamination and crack initiation around the sensor area, which may reduce the load carrying capacity of the host structure, reduce the sensing performance or lose the sensing capability of the embedded sensor. Based on the above, the embodiment of the invention adopts conductive ink without polymer matrix, and the sensor body is embedded into the prepreg layer by instillation technology to form the composite sensor, wherein the sensor body can be well impregnated by the prepreg, and the problem of mismatch of thermal behaviors between the sensor body and the prepreg layer does not exist. In addition, the shape of the sensor is not limited in the embodiment of the invention, and the sensor can be arranged according to actual needs. The composite sensor can be used in the fields of material structure health detection, human and machine motion detection, service life estimation of machines, supercapacitors, electromagnetic shielding and the like.
Meanwhile, the invention can also repeat the step S22 for a plurality of times to form a sensor body with a multi-layer structure, thereby forming the sensor body with preset thickness.
In step S24, in some embodiments, the curing temperature is 100-150 ℃, e.g., may be 100, 110, 120, 130, 140, or 150 ℃, etc.; the curing time is 60-120min, for example, 60, 70, 80, 90, 100, 110 or 120min, etc.
The following describes a preparation method of the composite sensor by using the prepreg in the composite sensor to include a first prepreg layer, a second prepreg layer and a third prepreg layer, wherein the sensor body is positioned between the second prepreg layer and the third prepreg layer, and the preparation method of the composite sensor includes the following steps:
preparing a second prepreg layer, and dripping the conductive ink without the polymer matrix onto the second prepreg layer, and drying to form a sensor body;
placing a wire on the sensor body;
stacking a first prepreg to a preset thickness to form a first prepreg layer (a base layer), and then arranging a second prepreg layer containing a sensor body and metal wires on the first prepreg layer, wherein the second prepreg layer is arranged away from the first prepreg layer or is adhered to the first prepreg layer;
and stacking a third prepreg on the second prepreg layer, or stacking the third prepreg on the sensor body and the metal wires to form the third prepreg layer, and drying and curing to obtain the composite sensor.
The first prepreg layer, the second prepreg layer and the third prepreg layer may be the same or different.
The following is a detailed description of specific examples.
Example 1
The preparation method of the conductive ink without the polymer matrix comprises the following steps in parts by mass:
adding 1 part of graphene oxide nano-sheets into 1 part of deionized water, and performing ultrasonic treatment for 30min to obtain graphene oxide dispersion liquid;
6 parts of Ti 3 C 2 Adding into 1 part of deionized water, and performing ultrasonic treatment for 30min to obtain Ti 3 C 2 A dispersion;
adding 0.1 part of sodium hydroxide into 0.025 part of deionized water, and stirring until the sodium hydroxide is dissolved to obtain a sodium hydroxide solution;
adding 10 parts of cysteine into 0.25 part of deionized water, and stirring for 15min to obtain cysteine dispersion;
mixing the graphene oxide dispersion liquid with Ti 3 C 2 Adding the dispersion liquid into the cysteine dispersion liquid, then adding sodium hydroxide solution, placing at a temperature of 95 ℃ for reaction for 6 hours, filtering to obtain hydrogel (black) containing reduced graphene oxide and MXene, and washing the hydrogel with brine and deionized water in sequence until the pH value of the hydrogel is 7;
and adding 30 parts of the washed hydrogel into 1 part of deionized water, stirring for 24 hours, and then performing ultrasonic treatment for 30 minutes to obtain the conductive ink without the polymer matrix.
Example 2 preparation of a composite sensor
Dropping the conductive ink without the polymer matrix prepared in the example 1 on an epoxy resin glass fiber prepreg (Easycomposites UK) layer (a second prepreg layer), and drying to form a sensor body;
two copper wires are placed in parallel on the sensor body, one ends of the two copper wires are connected with the sensor body, and the distance is 5mm;
providing an epoxy resin glass fiber prepreg layer (a first prepreg layer), and arranging the epoxy resin glass fiber prepreg layer (a second prepreg layer) containing the sensor body and the metal wires on the epoxy resin glass fiber prepreg layer (the first prepreg layer), wherein the epoxy resin glass fiber prepreg layer (the second prepreg layer) is arranged by being attached to the first prepreg layer;
and stacking epoxy resin glass fiber prepreg (third prepreg) on the sensor body and the copper wires to form an epoxy resin glass fiber prepreg layer (third prepreg), sealing in a vacuum bag, exposing the other ends of the two copper wires to the outside, vacuum drying for 15min, and curing at 120 ℃ for 90min to obtain the composite sensor, wherein the appearance of the composite sensor is shown in figure 1.
Comparative example 1
The only difference from example 2 is that the step of dropping the conductive ink without the polymer matrix was not performed, and the composite material was prepared.
And (3) testing:
(1) The composite sensor of example 2 was subjected to an interlaminar shear strength test with the composite material of comparative example 1, and the results are shown in fig. 2, in which the composite material (no sensor) corresponds to comparative example 1 and the composite material (with sensor) corresponds to example 2. It can be seen that the embedding of the sensor body in the invention does not reduce the mechanical properties of the composite material, that is, the embedding of the sensor retains the mechanical properties of the original prepreg layer.
(2) The composite sensor of example 2 was subjected to a sensitivity coefficient test and compared with the existing sensor, and the result is shown in fig. 3, and the composite sensor provided by the present invention has an excellent sensitivity coefficient compared with the existing sensor.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A polymer matrix-free conductive ink comprising a solvent, and reduced graphene oxide and MXene dispersed in the solvent, the reduced graphene oxide and MXene being covalently linked by a Ti-O-C bond.
2. The polymer matrix free conductive ink of claim 1 wherein the solvent is a polar solvent comprising at least one of water, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone.
3. A method of preparing a polymer matrix free conductive ink according to claim 1 or 2, comprising the steps of:
providing a graphene oxide dispersion and an MXene dispersion, the solvent of the graphene oxide dispersion and the MXene dispersion comprising at least water;
mixing the graphene oxide dispersion liquid and the MXene dispersion liquid to obtain a composite dispersion liquid;
adding a reducing agent into the composite dispersion liquid to perform a reduction reaction to obtain hydrogel containing reduced graphene oxide and MXene; or, adding a reducing agent and an alkaline substance into the composite dispersion liquid to perform a reduction reaction to obtain hydrogel containing reduced graphene oxide and MXene;
washing the hydrogel until the pH value of the hydrogel is neutral;
dispersing the washed hydrogel in a solvent to obtain the conductive ink without the polymer matrix.
4. The method according to claim 3, wherein the reducing agent comprises at least one of ascorbic acid, cysteine, hydrazine hydrate, dimethylhydrazine, sodium citrate, acetic acid hydride, sodium borohydride, halogen acid, fuming sulfuric acid.
5. The method according to claim 3, wherein the alkaline substance comprises at least one of sodium hydroxide and potassium hydroxide.
6. A method according to claim 3, wherein the temperature of the reduction reaction is 60-95 ℃ and the time of the reduction reaction is 6-12 hours.
7. The method of claim 3, wherein the MXene comprises Ti 3 C 2 、Ti 2 C、Ti 3 At least one of the CNs.
8. The composite sensor is characterized by comprising a prepreg layer, a sensor body embedded in the prepreg layer and a conductive wire connected with the sensor body, wherein the sensor body comprises reduced graphene oxide and MXene connected with the reduced graphene oxide through a Ti-O-C covalent bond.
9. The composite sensor of claim 8, wherein the conductive wire comprises at least one of a metal wire, a carbon nanotube fiber wire, a carbon fiber wire;
the prepreg comprises one of glass fiber prepreg, aramid fiber prepreg, carbon fiber prepreg and natural fiber-based prepreg.
10. A method of manufacturing a composite sensor according to claim 8 or 9, comprising the steps of:
providing a prepreg layer;
dropping the polymer matrix-free conductive ink according to any one of claims 1-2 or dropping the polymer matrix-free conductive ink prepared by the preparation method according to any one of claims 3-7 on the prepreg layer, and drying to form a sensor body;
a conductive wire is arranged on the sensor body;
and forming a prepreg layer on the sensor body and the conductive wire, and drying and curing to obtain the composite sensor.
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