CN112656409B

CN112656409B - Textile ion sensor and preparation method and application thereof

Info

Publication number: CN112656409B
Application number: CN202110023740.7A
Authority: CN
Inventors: 周杰; 马辉; 张剑; 周青青
Original assignee: Jiaxing University
Current assignee: Jiaxing University
Priority date: 2021-01-08
Filing date: 2021-01-08
Publication date: 2022-03-01
Anticipated expiration: 2041-01-08
Also published as: CN112656409A

Abstract

The invention provides a textile ion sensor and a preparation method and application thereof, and belongs to the technical field of textile sensing. The textile ion sensor provided by the invention comprises a fabric, and amino fullerene and reduced graphene oxide which are assembled on the fabric in a pi-pi stacking combination mode. The amino fullerene has the typical characteristic of electron-deficient aromatic hydrocarbon, and has strong electron-withdrawing capability and hydration capability in aqueous solution; meanwhile, the aminofullerene has different hydration abilities to different ions in the solution, which results in different binding abilities between different ions and the aminofullerene in the solution. Therefore, different ions or ion concentrations in the solution can generate certain difference when being combined with the amino fullerene; and then the textile ion sensor can realize the monitoring of ions in sweat. The invention also provides a preparation method of the textile ion sensor in the technical scheme, and the preparation method provided by the invention is simple to operate.

Description

Textile ion sensor and preparation method and application thereof

Technical Field

The invention relates to the technical field of textile sensing, in particular to a textile ion sensor and a preparation method and application thereof.

Background

Fabric-based sensors have the characteristics of good breathability, flexibility, knittability, low cost, and ease of application over large areas, making them important applications in many areas, such as health, sports, entertainment, and biomedical sciences. Particularly in the health field, these textile-based sensors allow detection and sensing of human body movements, such as temperature, skin moisture, heart rate, blood pressure, etc. The fabric sensor can be prepared by a coating method, an electroplating method, a dipping method, a roll baking method and the like. Metal matrix composites, organic conducting polymers and carbon based materials are commonly used to make these sensors. Among them, the most widely used carbon-based material is graphene, which is resistant to high and low temperatures, acids and alkalis, and has a large number of active groups on the surface to make it easily adhere to the surface of the fiber. Therefore, graphene plays an important role in the design and development of fabric-based sensors and is a hot spot of research.

Currently, fabric-based sensors fabricated from graphene are commonly used for strain sensing and human motion monitoring. Yellow et al (T.Huang, S.Yang, P.He, J.Sun, S.Zhang, D.Li, Y.Meng, J.ZHou, H.Tang, J.Liang, G.Ding, X.Xie, Phase-Separation-Induced PVDF/Graphene Coating on Fabrics heated Flexible Piezoelectric Sensors, ACS Applied Materials)&Interfaces 10(36) (2018) 30732-30740) mixes and disperses polyvinyl fluoride (PVDF) with graphene in N-methamphetamine, and then coats various fabrics (nylon, tissue, cotton, bamboo fiber and flax) which can output high voltage and have 34 V.N^-1The sensitivity and the test threshold value of 0.6mN have good monitoring effect on human body movement. Similarly, Liu et al (W.Liu, Y.Huang, Y.Peng, M.Walczak, D.Wang, Q.Chen, Z.Liu, L.Li, Stable Wearable string Sensors on Textiles by Direct Graphene Writing of Graphene, ACS Applied Nano Materials 3(1 (2020) 283) 293) use UV Direct processing of Graphene on polyimide fabric to prepare composite fabric with Strain sensing function, such fabric-based sensor surface having a large amount of three-dimensional porous Graphene, fabric resistance of only 20 Ω/square, and when the Strain is less than 4% (GFmax ═ 27), the sensor has good linearity, low threshold (Strain ═ 0.08%), high sensitivity, and high stability. Furthermore, graphene fabric-based sensors may also be used for other aspects of sensing, such as temperature and humidity. The Lee research team (T.Q.Trung, H.S.Le, T.M.L.Dang, S.Ju, S.Y.park, N.E.Lee, freesanding, Fiber-Based, Wearable Temperature Sensor with Tunable Thermal Index for Healthcare Monitoring,7 (2018)1800074) prepared graphene-Based fibers by a simple wet spinning process and then woven into various textiles to prepare Temperature sensors with wear resistance and Temperature regulation properties, which have a fast response speed (7s) and a fast Temperature recovery time (20s) and can maintain the responsiveness when subjected to external force tensile deformation. Li et al (B.Li, G.Xiao, F.Liu, Y.Qiao, C.M.Li, Z.Lu, A flexible hub sensor based on simple fabrics for human respiranti)on monitoring, Journal of Materials Chemistry C6 (16) (2018)4549-4554.) graphene oxide is attached to silk fabric using plating and spraying methods to prepare and assemble a sensitive moisture sensor that can accurately detect the respiratory rate of a human, including effectively distinguishing normal breathing, deep breathing and rapid breathing; at the same time, the fabric humidity sensor also has excellent bending resistance. Therefore, the fabric-based sensor has great application potential in the aspects of intelligent and wearable performance, and is expected to be further researched and developed in the health fields of medical treatment, medical monitoring and the like.

With the rapid development of economy and the continuous deterioration of environment, people pay more and more attention to the monitoring of physical health. As important human secretions, sweat contains a large amount of inorganic ions (Na) in addition to glucose and lactic acid⁺、K⁺、Mg⁺、Ca²⁺Etc.) that are closely related to blood pressure, cardiovascular function, muscle contraction, enzyme activation, and bone growth.

Therefore, the wearable fabric sensor is designed and developed, the accurate monitoring of ions in sweat on the surface of a human body is realized, the method has important significance on the life and health of the human body, and the development of disease prevention materials is further promoted.

Disclosure of Invention

In view of this, the present invention provides a textile ion sensor, and a method for manufacturing the same and an application thereof, and the textile ion sensor provided by the present invention can accurately detect ions in sweat, thereby realizing monitoring of human life and health.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a textile ion sensor, which comprises a fabric, amino fullerene and reduced graphene oxide assembled on the fabric in pi-pi accumulation.

Preferably, the mass ratio of the sum of the masses of the amino fullerene and the reduced graphene oxide to the fabric is (0.01-1): 100.

preferably, the mass ratio of the reduced graphene oxide to the amino fullerene is not less than 9.

Preferably, the mass ratio of the reduced graphene oxide to the amino fullerene is 19.

The invention also provides a preparation method of the textile ion sensor in the technical scheme, which comprises the following steps:

mixing amino fullerene with graphene oxide, and grinding to obtain an abrasive;

mixing the grinding material with a polar solvent to obtain a steeping liquor;

immersing the fabric into the impregnation liquid, and carrying out impregnation and padder to obtain a precursor;

and mixing the precursor with hydrazine hydrate, and carrying out reduction reaction to obtain the textile ion sensor.

Preferably, the mass percentage of the abrasive in the impregnation liquid is 0.01-1%.

Preferably, the dipping time is 1-60 min; the intensity of the padder is-0.1-0.5 MPa, and the speed is 1-5 m/min.

Preferably, the dipping and padder process is repeated 4-6 times.

Preferably, the temperature of the reduction reaction is 30-130 ℃ and the time is 0.2-5 h.

The invention also provides application of the textile ion sensor in the technical scheme or the textile ion sensor prepared by the preparation method in the technical scheme in the sweat monitoring field for non-disease diagnosis and treatment.

The invention provides a textile ion sensor, which comprises a fabric, amino fullerene and reduced graphene oxide assembled on the fabric in pi-pi accumulation. The amino fullerene has the typical characteristic of electron-deficient aromatic hydrocarbon, and has strong electron-withdrawing capability and hydration capability in aqueous solution; the aminofullerenes have different hydration capabilities for different ions in solution, which results in different binding capabilities between different ions and the aminofullerene in solution. Therefore, different ions or different ion concentrations in the solution are combined with the amino fullerene to generate certain difference, so that the textile ion sensor can monitor the ions in sweat, the reduced graphene oxide has good conductivity and plays a role in transmitting electrons, and the difference of the combining capacity of the amino fullerene and different ions can be well transmitted to a display end through the reduced graphene oxide. Further, the textile ion sensor can realize non-disease diagnosis and sweat monitoring for treatment.

The invention also provides a preparation method of the textile ion sensor in the technical scheme, and the preparation method provided by the invention is simple to operate and can be used for successfully preparing the textile ion sensor.

Drawings

FIG. 1 is an assembly schematic of a textile ion sensor provided by the present invention;

FIG. 2 is a scanning electron micrograph of a textile ion sensor;

FIG. 3 is a schematic view of the assembly of graphene sheets and fullerenes;

FIG. 4 is an XPS survey of unmodified cotton fiber, RGO/C60@ CF-0, RGO/C60@ CF-1, RGO/C60@ CF-2, RGO/C60@ CF-5, and RGO/C60@ CF-10;

FIG. 5 is a C1s spectrum of an unmodified cotton fiber fabric;

FIG. 6 is a C1s spectrum of RGO/C60@ CF-0;

FIG. 7 is a C1s spectrum of RGO/C60@ CF-1;

FIG. 8 is a C1s spectrum of RGO/C60@ CF-2;

FIG. 9 is a C1s spectrum of RGO/C60@ CF-5;

FIG. 10 is a C1s spectrum of RGO/C60@ CF-10;

FIG. 11 is a graph of the binding effect of RGO/C60@ CF on different cations;

FIG. 12 is a graph of the binding effect of RGO/C60@ CF on different anions;

FIG. 13 is a graph of the effect of RGO/C60@ CF-5 on different salt solutions;

FIG. 14 is a graph of the response of RGO/C60@ CF-5 to different sweat before and after 1000 bends at 180 degrees;

fig. 15 is a conceptual diagram of the application of the textile ion sensor.

Detailed Description

The textile ion sensor provided by the invention comprises a fabric, wherein the fabric is preferably a synthetic fiber, a natural fiber or a regenerated fiber; the synthetic fiber is preferably terylene, acrylon or chinlon; the natural fibers preferably comprise cotton fibers, hemp fibers, wool fibers or silk, and are further preferably cotton fibers; the regenerated fibers are preferably viscose fibers. In the invention, the gram weight of the fabric is preferably 50-200 g/m²More preferably 80 to 120g/m²。

The textile ion sensor provided by the invention comprises amino fullerene and reduced graphene oxide which are assembled on the fabric in a pi-pi stacking combination mode. In the invention, the mass ratio of the sum of the masses of the amino fullerene and the reduced graphene oxide to the fabric is preferably (0.01-1): 100, more preferably 0.12: 100, respectively; the mass ratio of the reduced graphene oxide to the amino fullerene is preferably not less than 9, and more preferably 19.

In the invention, the amino fullerene in the textile ion sensor is mainly embedded into the reduced graphene oxide sheet in a spherical form, so that a large number of nano-channels are formed for ion transmission.

mixing amino fullerene with graphene oxide, and grinding to obtain an abrasive;

mixing the grinding material with a polar solvent to obtain a steeping liquor;

In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.

The amino fullerene and the graphene oxide are mixed and ground to obtain the abrasive.

In the present invention, the time for the grinding is preferably 1 hour. In the present invention, the mass ratio of the graphene oxide to the aminofullerene is preferably not less than 9, and more preferably 19. In the present invention, the graphene oxide is preferably prepared by using Hummers method well known to those skilled in the art.

After the grinding material is obtained, the grinding material is mixed with a polar solvent to obtain the impregnation liquid. In the present invention, the polar solvent is preferably water. In the invention, the mixing is preferably carried out under the condition of ultrasound, and the frequency of the ultrasound is preferably 40-80 kHz; the time is preferably 0.2-2 h. In the invention, the mass percentage content of the abrasive in the impregnation liquid is preferably 0.01-1%, and more preferably 0.1%.

After the dipping solution is obtained, the fabric is immersed into the dipping solution for dipping and paddling to obtain the precursor. The dosage ratio of the fabric and the impregnating solution is not particularly limited, as long as the fabric can be sufficiently impregnated. In the invention, the soaking time is preferably 1-60 min; the intensity of the padder is preferably-0.1-0.5 MPa, and more preferably 0.2 MPa; the speed is preferably 1-5 m/min, and more preferably 1.5 m/min; the time of the padder is not particularly limited, and the padder can be used for keeping the retention rate of the fabric after padder to be 50-150%. In the invention, the dipping and padder are preferably repeated for 4-6 times, and more preferably 5 times; the process of repeating the dipping and padder is particularly preferably as follows: dip-padder-dip-padder … … dip-padder.

After the padder, the invention preferably further comprises drying the padred fabric, wherein the drying temperature is preferably 60 ℃, and the drying time is not particularly limited in the invention as long as the polar solvent can be dried.

After the precursor is obtained, the precursor and hydrazine hydrate are mixed for reduction reaction, and the textile ion sensor is obtained. The dosage ratio of the precursor and the hydrazine hydrate is not particularly limited, as long as the hydrazine hydrate can be ensured to fully impregnate the precursor. In the invention, the temperature of the reduction reaction is preferably 30-130 ℃, and more preferably 90 ℃; the time is preferably 0.2 to 5 hours, and more preferably 3 hours.

After the reduction reaction is finished, the invention preferably also comprises washing and drying the obtained reduction reaction system in sequence; the washing reagent is preferably water, and the washing times are preferably 2-5 times; the temperature of the drying is preferably 60 ℃, and the time of the drying is not particularly limited in the present invention as long as the polar solvent can be completely removed.

Fig. 1 is an assembly schematic diagram of a textile ion sensor provided by the present invention, in which a fabric is immersed in an immersion liquid containing an amino fullerene and graphene oxide, the fabric is filled with the amino fullerene and graphene oxide, and then paddled to obtain a precursor; and carrying out reduction reaction on the precursor to obtain the textile ion sensor.

The invention also provides the application of the textile ion sensor in the technical scheme or the textile ion sensor obtained by the preparation method in the technical scheme in the sweat monitoring field for non-disease diagnosis and treatment. In the present invention, when the textile ion sensor is applied to monitoring sweat, it preferably comprises the following steps:

and dropping the sweat on a textile ion sensor, wherein the textile ion sensor is connected with an electric signal output device to obtain an electric signal of the sweat.

The textile ion sensor provided by the invention and the preparation method and application thereof are described in detail below with reference to the examples, but the examples should not be construed as limiting the scope of the invention.

Examples

The amino fullerene and the graphene oxide are mixed according to different mass ratios of 0: 100. 1: 99. 2: 98. 5: 95. 10: 90, mixing and grinding for 1 hour to obtain the grinding material;

mixing the grinding material and water for 1 hour under the ultrasonic condition to respectively prepare soaking solutions with the mass percentage of 0.1%;

mixing 5X 10cm²Cotton fiber (gram weight 80 g/m)²) Soaking in the soaking solution for 10min, and then passing through padder (pressure of 0.2MPa, speed of 1.5 m-Minutes), after repeating the above dipping-padder 5 times; the rolling residual rate is 120%, and the fabric after rolling is dried at 60 ℃ to obtain a precursor;

immersing the precursor into hydrazine hydrate, and reducing for 3h at 90 ℃; finally, washing with deionized water and drying at 60 ℃ to obtain the textile ion sensor; designated RGO/C60@ CF-0, RGO/C60@ CF-1, RGO/C60@ CF-2, RGO/C60@ CF-5, and RGO/C60@ CF-10, respectively.

Performance characterization

Fig. 2 is a scanning electron micrograph of a textile ion sensor, wherein: the picture a is a scanning electron microscope picture of unmodified cotton fiber, the picture b is a scanning electron microscope picture of RGO/C60@ CF-0, the picture C is a scanning electron microscope picture of RGO/C60@ CF-1, the picture d is a scanning electron microscope picture of RGO/C60@ CF-2, the picture e is a scanning electron microscope picture of RGO/C60@ CF-5, and the picture f is a scanning electron microscope picture of RGO/C60@ CF-10. As can be seen from the a diagram: the surface of the original cotton fiber fabric is adhered with some foreign particles, so that the fabric is not absolutely smooth and clean; the cotton fiber fabric is used as a natural fiber, the surface texture of the cotton fiber fabric is also clear and visible, and the cotton fiber fabric belongs to a normal cotton structure; however, at high magnification (small panels in panel a), it can be seen that: the surface of the cotton fiber fabric is still relatively smooth and has no obvious defects or protrusions. As can be seen from the b diagram: the surface of the cotton fiber fabric loaded with the reduced graphene oxide is covered by a layer of disordered reduced graphene oxide; and part of the surface of the cotton fiber fabric presents an ordered coating, and the aggregation and hardening phenomena of the reduced graphene oxide exist. However, as can be clearly seen from the c-e diagrams: the surface of the cotton fiber fabric is coated with a reduced graphene oxide/amino fullerene layer, and becomes orderly and uniform along with the increase of amino fullerene. This is probably because when the aminofullerene is not introduced into the cotton fiber fabric, the reduced graphene oxide sheets are accumulated on the surface of the cotton fiber fabric in a disordered state during the impregnation process, thereby macroscopically causing disordered distribution of the reduced graphene oxide on the surface of the cotton fiber fabric. When aminofullerenes are incorporated into cotton fiber fabrics, pi-pi bond stacking between the reduced graphene oxide and the aminofullerenes creates interactions, and these binding forces cause the aminofullerene spheres to act as a "mini-binder" between the reduced graphene oxide sheets, creating a tendency to bind orderly rather than to stack randomly. Therefore, the aminofullerene and reduced graphene oxide coating shows good uniformity on the surface of the cotton fiber fabric; the introduction of the amino fullerene results in the conversion of reduced graphene oxide sheets on cotton fiber fabrics from a disorganized to an ordered structure. However, as the proportion of aminofullerenes continues to increase to some extent, the cotton fiber fabric surface shows a small amount of stacking and non-uniformity (as in the f-plot in fig. 2); this is probably due to the fact that at relatively high concentrations of aminofullerene, the aminofullerene agglomerates on its own, which leads to a somewhat reduced "mini-binder" effect.

Fig. 3 is a schematic view of the assembly of graphene sheets and fullerenes.

FIG. 4 is an XPS survey of unmodified cotton fiber, RGO/C60@ CF-0, RGO/C60@ CF-1, RGO/C60@ CF-2, RGO/C60@ CF-5, and RGO/C60@ CF-10; FIG. 5 is a C1s spectrum for an unmodified cotton fabric, FIG. 6 is a C1s spectrum for RGO/C60@ CF-0, FIG. 7 is a C1s spectrum for RGO/C60@ CF-1, FIG. 8 is a C1s spectrum for RGO/C60@ CF-2, FIG. 9 is a C1s spectrum for RGO/C60@ CF-5, and FIG. 10 is a C1s spectrum for RGO/C60@ CF-10. As shown in fig. 4, without the amino fullerene modification, the surface of the cotton fiber fabric only contains elements C and O; after the amino fullerene is added, the N element appears on the surface of the cotton fiber fabric, and the content of the N element is shown in the table 1; the trace amount of N on the surfaces of Cotton Fabrics (CF) and RGO/C60@ CF-0 may be caused by impurities on the surfaces of cotton fabrics. However, when the content of the aminofullerene is multiplied, the content of the N element on the surface of the cotton fiber fabric is not increased by a corresponding factor but is only slightly increased, which is probably because a large number of the aminofullerene spheres are not attached to the surface of the reduced graphene oxide sheets but are embedded between the insides of the reduced graphene oxide sheets during the impregnation process. Due to limitation of XPS depth of detection (10 nm), a large number of internal amino fullerenes have not been fully detected. Thus, it can be seen from the C1s spectra of fig. 5-10: peaks at 284.8ev (peak 1), 286ev (peak 2), 287.6ev (peak 3) and 289.2ev (peak 4) correspond to C-C/C-H, C-O/C-N, C ═ O and O-C ═ O, respectively. For peak 2, which represents the C-O/C-N bond, the raw cotton fabric surface had many hydroxyl groups, with a proportion as high as 49.9%. For RGO/C60@ CF-0, the proportion of peak 2 is only 23.4%. When an aminofullerene was added during the impregnation, the mass percentages of peak 2 of RGO/C60@ CF-1, RGO/C60@ CF-2, RGO/C60@ CF-5 and RGO/C60@ CF-10 were 25.4%, 26.8%, 27.7% and 29.1%, respectively. The results show that the proportion of peak 2 is only slightly increased, which is also consistent with the above elemental content analysis results. In other words, the amino fullerene spheres are mainly embedded in the reduced graphene oxide sheets, thereby forming a large number of nanochannels for ion transport.

TABLE 1 elemental content of cotton fiber fabric surface

Binding Effect of RGO/C60@ CF on different ions

RGO/C60@ CF was immersed in a solution having an ion concentration of 100mmol/L and the response of RGO/C60@ CF to different sized ions was observed.

FIG. 11 is a graph of the binding effect of RGO/C60@ CF on different cations. As can be seen from fig. 11: the resistivity of the reduced graphene oxide modified cotton fiber fabric (RGO/C60@ CF-0) did not change significantly when combined with cations of different radii, indicating that the reduced graphene oxide sheets on the cotton fiber fabric were not reactive to different cations. Likewise, when 1% of an aminofullerene was introduced into the reduced graphene oxide channel (RGO/C60@ CF-1), no significant reaction of the modified cotton fiber fabric to cations of different radii was observed. However, when the mass content of the aminofullerene is increased to 2% or even 5% (RGO/C60@ CF-2, RGO/C60@ CF-5), the resistivity of the modified cotton fabric increases with the radius of the cation, and when the mass content of the fullerene is 5%, the change in resistivity is more pronounced because the volume of the cation is larger, such as Gd, when the charge number of the cation is the same, the_m ⁺The greater the deformability of the ions. Thus, larger cations are more likely to undergo dipole-dipole interactions with aminofullerenes, which have the electron-deficient characteristics typical of aromatic hydrocarbons. However, when the content of aminofullerene was increased to 10% (RGO/C60@ CF-10), modification was carried outCotton fiber fabrics do not react significantly to cations of different radii. In the above scanning electron microscope analysis, it is mentioned that when the content of the amino fullerene is too high, the amino fullerene spheres may have a certain aggregation phenomenon, which may cause the distribution uniformity of the reduced graphene oxide on the surface of the cotton fiber fabric to decrease, thereby causing the response capability of the cotton fiber fabric to ions to decrease.

FIG. 12 is a graph of the binding effect of RGO/C60@ CF on different anions, as can be seen in FIG. 12: with the increase of the content of the amino fullerene, the sensitivity of the modified cotton fiber fabric to different anions is obviously improved, especially when the content of the amino fullerene is 5 percent. However, when the content of the aminofullerene is increased to 10%, the sensitivity is slightly decreased for the same reason as described above. For anions (Cl) of different radii^-、I^-、NO₃ ^-、ClO₄ ^-) The resistivity of RGO/C60@ CF also has the same rule of variation as ions. Typically, e.g., ClO₄ ^-It not only has the largest ionic radius and the strongest dispersion force, but also has the weakest hydration ability in aqueous solution; thus, it is easier to form dipole-dipole interactions with the amino fullerene spheres, resulting in the highest resistivity.

The sensitivity of the textile ion sensor is researched, the RGO/C60@ CF-5 with the best effect is taken as a research target, and three representative salt solutions (NaCl, Gd) with different concentrations are analyzed_mCl、NaClO₄) The effect on RGO/C60@ CF-5 resistivity is shown in FIG. 13. FIG. 13 is a graph of the effect of RGO/C60@ CF-5 on different salt solutions. As can be seen from fig. 13: the resistivity of RGO/C60@ CF-5 gradually decreased with increasing salt solution concentration. In addition, Gd was added to the NaCl solution as a control_mCl and NaClO₄The resistivity of the solution was higher than that of NaCl solution of the same ion concentration, and this rule was still evident even if the ion concentration was as low as 1mmol/L, which is consistent with the above analysis. The textile ion sensor provided by the invention has an excellent sensing function and can detect various ion concentrations.

Application of textile ion sensor

Sweating is a common physiological phenomenon. It is a way of thermoregulation, evaporation and heat dissipation, and is also a reaction of emotions. Sweat glands are one of the most developed human organs and are present throughout the body in the dermis of the skin. In traditional Chinese medicine, sweat, tears and saliva are collectively called body fluid, and sweating is considered as an important means for diagnosing diseases. Thus, the response capabilities of textile ion sensors were analyzed using three sweat (pH 4.3, 6.5 and 8.0), as shown in fig. 14, which is a graph of the response of RGO/C60@ CF-5 to different sweat before and after 1000 bends at 180 °. As can be seen from fig. 14: in each sweat test, the resistivity of the textile ion sensor increased with increasing aminofullerene content, with the highest resistivity being at 5% aminofullerene mass content, especially in sweat at pH 6.5. Furthermore, RGO/C60@ CF-5 has the most significant effect on the response effects of three different sweat, with a significant difference in resistivity from the three sweat. In addition, the textile ion sensor has good flexibility, so that the textile ion sensor is difficult to bend in practical application. Thus, the effect of bending on the textile ion sensor ion response was tested, as shown in fig. 14. The results show that the resistivity of the textile ion sensor increases only slightly for each sweat even after 1000 folds of 180 °. For example, RGO/C60@ CF-5 increased the resistivity of three sweat regions by only 4.3% (pH 4.3) and 3.3% (pH 6.5) and 4.2% (pH 8.0), respectively, before and after the bend test. The result shows that the textile ion sensor has good durability. Therefore, based on all the ion response experimental results, the textile ion sensor RGO/C60@ CF-5 has potential application value in monitoring human sweat for non-disease diagnosis and treatment purposes. By being designed into a wearable textile, the evaluation on human health is expected to be realized through sweat monitoring. Fig. 15 is a conceptual diagram of the application of the textile ion sensor.

As can be seen from the above examples, the textile ion sensor RGO/C60@ CF-5 provided by the present invention reacts well to different ions due to the ionic specificity of the aminofullerene itself. The amino fullerene spheres have electronic defects and can perform dispersive interaction with ions with different radiuses to different degrees, so that the modified cotton fiber fabric has an ion sensing function. The larger the ionic radius, the larger the resistivity. RGO/C60@ CF-5 still showed good sensitivity when the ion concentration was only 1 mmol/L. In addition, the textile ion sensor also shows different sensing characteristics of different types of sweat, and the sensitivity of the textile ion sensor is slightly changed even after being bent at 180 degrees for 1000 times, which shows that the textile ion sensor has excellent flexibility. The textile ion sensor RGO/C60@ CF provided by the invention provides inspiration for the design of the next-generation sensitive and highly flexible intelligent ion sensor.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A textile ion sensor comprising a fabric, an aminofullerene and reduced graphene oxide assembled on the fabric in pi-pi stacking.

2. The textile ion sensor according to claim 1, wherein the mass ratio of the sum of the masses of the aminofullerene and the reduced graphene oxide to the mass of the textile fabric is (0.01-1): 100.

3. the textile ion sensor according to claim 1 or 2, wherein the mass ratio of the reduced graphene oxide to the aminofullerene is not less than 9.

4. The textile ion sensor of claim 3, wherein the mass ratio of reduced graphene oxide to aminofullerene is 19.

5. The method for preparing the textile ion sensor according to any one of claims 1 to 4, comprising the following steps:

mixing amino fullerene with graphene oxide, and grinding to obtain an abrasive;

mixing the grinding material with a polar solvent to obtain a steeping liquor;

6. The preparation method according to claim 5, wherein the mass percentage of the abrasive in the impregnating solution is 0.01-1%.

7. The method according to claim 5, wherein the time for the immersion is 1 to 60 min; the intensity of the padder is-0.1-0.5 MPa, and the speed is 1-5 m/min.

8. The method according to claim 5 or 7, wherein the dipping and rolling process is repeated 4 to 6 times.

9. The preparation method according to claim 4, wherein the temperature of the reduction reaction is 30-130 ℃ and the time is 0.2-5 h.

10. Use of a textile ion sensor according to any one of claims 1 to 4 or obtained by a method of manufacture according to any one of claims 5 to 9 in the field of monitoring sweat for non-disease diagnostic and therapeutic purposes.