阅读说明：本技术 电热织物、氧化石墨烯气凝胶及其制备方法与应用 (Electrothermal fabric, graphene oxide aerogel and preparation method and application thereof ) 是由 王宝林 王金泉 于 2021-09-23 设计创作，主要内容包括：本申请公开了氧化石墨烯气凝胶及其制备方法、电热织物及应用。该制备方法包括：配制含有改性棉纤维、氧化石墨烯的第一溶液,以及含有纳米电气石的第二溶液；混合第一溶液和所述第二溶液,分散,并向分散的溶液中通入入洁净空气,同时滴入碱液调整pH值至10；转入密封条件下180℃处理10h,得到反应物；将所述反应物经过冷冻干燥,即可得到氧化石墨烯气凝胶。以此构建电热织物,该电热织物具有优异的电热性能,升温快,电热功率低,能耗地,电热作用持久,具有作为可穿戴设备,尤其是床垫面料的广泛应用前景。(The application discloses a graphene oxide aerogel, a preparation method thereof, an electrothermal fabric and application. The preparation method comprises the following steps: preparing a first solution containing modified cotton fibers and graphene oxide and a second solution containing nano tourmaline; mixing the first solution and the second solution, dispersing, introducing clean air into the dispersed solution, and simultaneously dropping alkali liquor to adjust the pH value to 10; processing for 10h at 180 ℃ under a sealed condition to obtain a reactant; and freeze-drying the reactant to obtain the graphene oxide aerogel. The electric heating fabric is constructed by the method, has excellent electric heating performance, is quick in temperature rise, low in electric heating power, low in energy consumption and lasting in electric heating effect, and has wide application prospect as wearable equipment, especially mattress fabric.)

1. The preparation method of the graphene oxide aerogel for generating the electrothermal function comprises the following steps:

preparing a first solution containing modified cotton fibers and graphene oxide and a second solution containing nano tourmaline;

mixing the first solution and the second solution, dispersing, introducing clean air into the dispersed solution, and simultaneously dropping alkali liquor to adjust the pH value to 10;

processing for 10h at 180 ℃ under a sealed condition to obtain a reactant;

and freeze-drying the reactant to obtain the graphene oxide aerogel.

2. The preparation method according to claim 1, wherein the mass concentration of the modified cotton fiber in the first solution is 4 to 10 wt%, and the mass concentration of the graphene oxide is 0.1 to 0.23 wt%.

3. The preparation method according to claim 1, wherein the mass concentration of the nano tourmaline in the second solution is 0.5-2%.

4. The method according to claim 1, wherein the mixing volume ratio of the first solution to the second solution is (2.5-4) to 1.

5. The method according to claim 1, wherein the clean air is introduced at a flow rate of 0.26 to 0.64 cfm.

6. The preparation method according to claim 1, wherein the preparation process of the modified cotton fiber specifically comprises the following steps:

dispersing absorbent cotton in an acetone solution, acidifying the absorbent cotton by a hypochlorous acid solution at the temperature of 65 ℃, and then adding formamide for modification at the temperature of 75 ℃ to obtain the modified cotton fiber.

7. The method according to claim 6, wherein the hypochlorous acid solution has a concentration of 2.0 to 3.0M.

8. Graphene oxide aerogel prepared by the preparation method according to any one of claims 1 to 7.

9. An electrothermal fabric, comprising a fireproof outer layer, a graphene oxide aerogel layer and a waterproof inner layer which are sequentially stacked, wherein the graphene oxide aerogel layer is made of the graphene oxide aerogel according to claim 8.

10. Use of the graphene oxide aerogel according to claim 8 in wearable electrothermal fabrics, electrothermal devices.

Technical Field

The application relates to the technical field of electric heating fabrics, in particular to an electric heating fabric, graphene oxide aerogel and a preparation method and application thereof.

Background

As a novel material, the graphene has the excellent characteristics of high Young modulus, high breaking stress, high carrier mobility, high thermal conductivity, large specific surface area, high light transmittance and the like, and has a wide application prospect in the fields of multifunctional composite materials, flexible wearable equipment, transparent electronic devices, new energy batteries, seawater desalination, biomedical treatment and the like. The aerogel prepared from the graphene has excellent heat-insulating property, particularly has a special continuous network connection hole structure in the aerogel, can reduce the weight of a protective fabric system to a certain extent, and has better moisture permeability and air permeability than the traditional heat protective fabric, so that the probability of heat stress of a wearer is reduced. The graphene aerogel has the advantages of high specific surface area, high porosity, high electrical conductivity, good transverse thermal conductivity, good mechanical strength and the like. Under the heat exposure condition, on the one hand, graphite alkene can quick heat conduction reduce the heat accumulation on fabric surface, and on the other hand aerogel structure can hinder external heat transfer to inside human skin betterly.

Disclosure of Invention

Based on the defects of the current domestic and foreign research and the current domestic development requirement, the application aims to develop the functions of the graphene aerogel, expand the application range of the graphene aerogel and play the application value of the graphene aerogel in the technical field of electrothermal fabrics.

In a first aspect, the embodiment of the application discloses a preparation method of a graphene oxide aerogel for generating an electric heating function, comprising the following steps:

preparing a first solution containing modified cotton fibers and graphene oxide and a second solution containing nano tourmaline;

mixing the first solution and the second solution, dispersing, introducing clean air into the dispersed solution, and simultaneously dropping alkali liquor to adjust the pH value to 10;

processing for 10h at 180 ℃ under a sealed condition to obtain a reactant;

and freeze-drying the reactant to obtain the graphene oxide aerogel.

In the embodiment of the application, in the first solution, the mass concentration of the modified cotton fiber is 4-10 wt%, and the mass concentration of the graphene oxide is 0.1-0.23 wt%.

In the embodiment of the application, the mass concentration of the nano tourmaline in the second solution is 0.5-2%.

In the embodiment of the application, the mixing volume ratio of the first solution to the second solution is (2.5-4): 1.

In the embodiment of the application, the flow rate of the clean air is 0.26-0.64 cfm.

In the embodiment of the present application, the preparation process of the modified cotton fiber specifically includes:

dispersing absorbent cotton in an acetone solution, acidifying the absorbent cotton by a hypochlorous acid solution at the temperature of 65 ℃, and then adding formamide for modification at the temperature of 75 ℃ to obtain the modified cotton fiber.

The method according to claim 6, wherein the hypochlorous acid solution has a concentration of 2.0 to 3.0M.

In a second aspect, the present application discloses a graphene oxide aerogel prepared by the preparation method described in the first aspect.

The embodiment of the application discloses electric heat fabric, including the fire prevention skin, the graphene oxide aerogel layer and the waterproof inlayer that stack gradually the setting, the graphene oxide aerogel layer be the second aspect the preparation of graphene oxide aerogel forms.

In a fourth aspect, the embodiment of the application discloses an application of the graphene oxide aerogel in wearable electrothermal fabrics and electrothermal equipment.

In the embodiment of the present application,

compared with the prior art, the application has at least the following beneficial effects:

the application takes graphene oxide, modified cotton fiber and nano tourmaline as raw materials, and prepares a unique graphene oxide aerogel by controlling preparation steps and conditions, and provides an electrothermal fabric constructed by graphene oxide, wherein the electrothermal fabric has excellent electrothermal performance, fast heating, low electrothermal power, low energy consumption and lasting electrothermal effect, and has wide application prospect as wearable equipment, especially mattress fabric.

Drawings

Fig. 1 is an SEM image of a graphene oxide aerogel provided in example 1 of the present application.

Fig. 2 is an infrared spectrum of the graphene oxide aerogel and graphene oxide provided in embodiment 1 of the present application.

Fig. 3 is an XPS spectrogram of the modified cotton fiber, the graphene oxide aerogel and the graphene oxide provided in embodiment 1 of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

Preparation of modified Cotton fibers

1. Preparation process

One specific example 1 was prepared as follows:

1) cotton fibers (100% absorbent cotton, Wahleu sanitary materials Co., Ltd.) were dried and weighed to about 4.2g, 1000mL of acetone was added, and ultrasonic cleaning was performed at 30 ℃ for 40min to sufficiently disperse the cotton fibers.

2) Taking out the cotton fiber, transferring the cotton fiber to a three-neck flask (500mL) provided with a stirrer, a condenser and a thermometer, fixing the three-neck flask in an oil bath pot, adding 300mL of 2M hypochlorous acid solution into the flask, adjusting the temperature of the oil bath pot to 65 ℃, reacting for 5 hours, filtering, removing liquid, and retaining the cotton fiber;

3) drying the cotton fiber in an oven at 45 ℃ for 12h, transferring the cotton fiber into the three-neck flask (500mL) provided with the stirrer, the condenser and the thermometer again, fixing the three-neck flask in an oil bath pot, adding a formamide solution of 250m1 into the flask, adjusting the temperature of the oil bath pot to 75 ℃, and reacting for 5h to obtain the modified cotton fiber. And in the reaction process, observing the color of the solution every 1h, taking out the modified cotton fiber according to different reaction times, cleaning the surface by using acetone, putting the surface into an oven for drying at 50 ℃ for 12h, taking out a sample, and performing performance detection and structure characterization.

The modified cotton fiber of example 2 was carried out as follows:

step 1) is the same as example 1, and step 2) is: taking out the cotton fibers, transferring the cotton fibers into a three-neck flask, adding 300mL of 2.5M hypochlorous acid solution into the flask, adjusting the temperature of an oil bath pot to 60 ℃, reacting for 4 hours, filtering, removing liquid, and keeping the cotton fibers; step 3) is the same as in example 1.

The modified cotton fiber of example 3 was carried out as follows:

step 1) is the same as example 1, and step 2) is: taking out the cotton fibers, transferring the cotton fibers into a three-neck flask, adding 300mL of 3.0M hypochlorous acid solution into the flask, adjusting the temperature of an oil bath pot to 57 ℃, reacting for 4 hours, filtering, removing liquid, and keeping the cotton fibers; step 3) is the same as in example 1.

The modified cotton fiber of comparative example 1 was carried out as follows:

step 1) is the same as example 1, and step 2) is: taking out the cotton fibers, transferring the cotton fibers into a three-neck flask, adding 300mL of 2.0M nitric acid solution into the flask, adjusting the temperature of an oil bath pot to 65 ℃, reacting for 5 hours, filtering, removing liquid, and keeping the cotton fibers; step 3) is the same as in example 1.

The modified cotton fiber of comparative example 2 was carried out as follows:

step 1) and step 2) are the same as in example 1, and step 3 is: drying the cotton fiber, transferring the cotton fiber to a three-neck flask, adding 250mL of ethylenediamine into the three-neck flask, adjusting the temperature of an oil bath to 70 ℃, and reacting for 5 hours to obtain the modified cotton fiber.

2. Performance detection and structural characterization

Monofilament tensile strength analysis:

two ends of the modified cotton fiber are respectively adhered to different photo paper, the cotton fiber is approximately parallel to the photo paper, a fiber strength instrument is adopted to respectively clamp the two photo paper for tensile strength test, and the modified cotton fiber is subjected to monofilament tensile strength test according to ASTM-D3379 Standard high modulus monofilament Material tensile Strength and Young modulus test method.

Interlaminar shear strength analysis:

placing modified cotton fiber in a polytetrafluoroethylene template groove with a structure of 2mm multiplied by 10mm multiplied by 100mm, sequentially and uniformly coating an oil-containing release agent and epoxy resin (the proportion of the epoxy resin to a curing agent is 3:1), then compacting by using a toughened glass plate, placing in a drying box, setting the temperature of the drying box at 80 ℃, and keeping the time for 12 hours. And soaking the cured modified cotton fiber resin sample in liquid nitrogen for 6h, taking out the sample, punching the sample by using a universal tester, and measuring the interlaminar shear strength by using a short beam method according to the standard JC/T773-2010/IS 014130: 1997.

The analysis results are shown in table 1, and the results are statistically collated by data analysis using Excel 2013 and SPSS 22.0 statistical software as experimental data, each data is measured several times and expressed by mean value and standard deviation thereof, and single-factor analysis of variance (One-way ANOVA) and DunCan's multiple comparison are respectively performed with SPSS 22.0, and marked for significant difference. As can be seen from the results in table 1, the modified cotton fibers prepared in examples 1 to 3 had both significantly greater monofilament tensile strength and interlaminar shear strength than the modified cotton fibers prepared in comparative examples 1 to 2.

TABLE 1

Detailed description of the preferred embodiments	Tensile Strength of monofilament (GPa)	Interlaminar shear strength (MPa)
			Example 1	4.92±0.14a	62.05±3.15a
Example 2	4.96±0.05a	63.62±2.36a
			Example 3	4.90±0.09a	62.84±1.67a
Comparative example 1	4.42±0.06b	53.21±1.34b
			Comparative example 2	4.39±0.14b	54.37±2.02b

Preparation of graphene oxide aerogel

1. Preparation process

The graphene oxide aerogel of example 1 was prepared as follows:

1) preparing a graphene oxide (GO for short, the transverse size of 20 microns, pioneer nano company) suspension and a nano tourmaline suspension (T for short, 50000 meshes, Lingshou brocade platinum ore product processing factories) by using deionized water respectively, wherein the mass concentration of the graphene oxide suspension is 4 wt%, the modified cotton fiber prepared in the example 1 is added into the graphene oxide suspension, so that the mass concentration of the modified cotton fiber is 0.1 wt%, the mass concentration of the nano tourmaline suspension is 1.5 wt%, and the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

2) diluting the mixed solution by 1 time, performing ultrasonic treatment for 1h to fully disperse the mixed solution, introducing clean air into the solution to generate bubbles, wherein the introduction flow of the clean air is 0.5cfm, then dripping 0.2M sodium hydroxide solution into the solution, continuously stirring until the pH value of the solution reaches 10, transferring the system into a high-pressure reaction kettle, and performing hydrothermal jacket treatment at 180 ℃ for 10h under a sealed condition to finish the reaction;

3) and placing the reacted reactant into a freezing box for ultralow temperature freezing for 12 hours, and continuously placing the frozen substance into a freeze dryer for freeze drying for 24 hours to obtain the graphene oxide aerogel.

The graphene oxide aerogel preparation implementation processes of example 2, example 3, comparative example 1 and comparative example 2 are all the same as example 1 except that example 2, example 3, comparative example 1 and comparative example 2 all use their own prepared modified cotton fibers in the graphene oxide aerogel preparation implementation processes.

The graphene oxide aerogel of example 4 was prepared as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 7 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of example 5 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 10 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of example 6 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.15%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of example 7 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.23%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel of example 8 was prepared as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the nano tourmaline suspension contains nano tourmaline with the mass concentration of 0.5%; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of example 9 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the nano tourmaline suspension liquid contains nano tourmaline with the mass concentration of 2.0 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel of example 10 was prepared as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 2.5: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of example 11 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 4: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of example 12 was carried out as follows:

1) same as in example 1.

2) Carrying out ultrasonic treatment on the mixed solution for 1h to fully disperse, simultaneously introducing clean air with the flow of 0.26cfm, simultaneously dripping 0.2M sodium hydroxide, continuously stirring until the pH value reaches 10, and then transferring the mixed solution into a high-temperature reaction kettle to react for 10h at 180 ℃;

3) same as in example 1.

The graphene oxide aerogel preparation of example 13 was carried out as follows:

1) same as in example 1.

2) Carrying out ultrasonic treatment on the mixed solution for 1h to fully disperse, simultaneously introducing clean air with the flow of 0.64cfm, simultaneously dripping 0.2M sodium hydroxide, continuously stirring until the pH value reaches 10, and then transferring the mixed solution into a high-temperature reaction kettle to react for 10h at 180 ℃;

3) same as in example 1.

The graphene oxide aerogel preparation of comparative example 3 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains 3 wt% of graphene oxide, and the graphene oxide suspension contains 0.1 wt% of the modified cotton fiber prepared in example 1; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 4 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains 11 wt% of graphene oxide, and the graphene oxide suspension contains 0.1 wt% of the modified cotton fiber prepared in example 1; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 5 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.08%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 6 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.25%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 7 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the nano tourmaline suspension contains nano tourmaline with the mass concentration of 0.4%; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 8 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the nano tourmaline suspension liquid contains nano tourmaline with the mass concentration of 2.1 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 3: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 9 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 2: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 10 was carried out as follows:

1) respectively preparing a graphene oxide suspension and a nano tourmaline suspension; wherein the graphene oxide suspension contains graphene oxide with a mass concentration of 4 wt%, and the graphene oxide suspension contains the modified cotton fiber prepared in example 1 with a mass concentration of 0.1%; the mass concentration of the nano tourmaline suspension is 1.5 percent; the mixing volume ratio of the graphene oxide suspension to the nano tourmaline suspension is 4.5: 1;

step 2) and step 3) are the same as in example 1.

The graphene oxide aerogel preparation of comparative example 11 was carried out as follows:

1) same as in example 1.

2) Carrying out ultrasonic treatment on the mixed solution for 1h to fully disperse, simultaneously introducing clean air with the flow of 0.25cfm, simultaneously dripping 0.2M sodium hydroxide, continuously stirring until the pH value reaches 10, and then transferring the mixed solution into a high-temperature reaction kettle to react for 10h at 180 ℃;

3) same as in example 1.

The graphene oxide aerogel preparation of comparative example 12 was carried out as follows:

1) same as in example 1.

2) Carrying out ultrasonic treatment on the mixed solution for 1h to fully disperse, simultaneously introducing clean air with the flow of 0.65cfm, simultaneously dripping 0.2M sodium hydroxide, continuously stirring until the pH value reaches 10, and then transferring the mixed solution into a high-temperature reaction kettle to react for 10h at 180 ℃;

3) same as in example 1.

2. Performance analysis method

SEM analysis: graphene oxide aerogels prepared in examples 1 to 13 and comparative examples 1 to 12 were used as samples by a Quanta FEG 250 electron scanning microscope manufactured by FEI Instruments, usa, and after being sprayed with gold, the conductive adhesive was adhered to a sample metal plate, and the surface morphology of the sample metal plate was obtained by scanning an electrothermal fabric in a vacuum environment.

The chemical composition of the prepared graphene oxide aerogel was analyzed using fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS).

3. Analysis results

Table 2 preparation of graphene oxide aerogels

The conditions associated with the processes of the steps of the graphene oxide aerogel prepared in each of examples 1 to 13 and comparative examples 1 to 12 are shown in table 1, wherein GO represents the concentration of the graphene oxide solution, CN represents the concentration of the modified cotton fiber contained in the graphene oxide solution, and Tourmaline represents the concentration of the nano Tourmaline solution.

Results the graphene oxide aerogels prepared in examples 1 to 13 and comparative examples 1 to 12, respectively, all obtained the nano tourmaline particles doped and also compounded with the modified cotton fibers, which provides help for the graphene oxide aerogels to obtain the relevant mechanical and electrical heating properties.

As shown in the SEM image of fig. 1, the graphene oxide aerogel is in a foam structure, the pores are from tens to hundreds of microns, the spherical bright spots in the diagram are spherical nano tourmaline particles with a size of 20-30 nm, and the modified cotton fibers in the linear shape in the diagram are uniformly distributed in the pores of the graphene oxide aerogel, which indicates that the graphene oxide aerogel prepared in the embodiment of the present application integrates the nano tourmaline particles into the result, and the modified cotton fibers support the graphene oxide aerogel and improve the strength of the graphene oxide aerogel.

FIG. 2 is an infrared spectrum. Due to the doping of the graphene oxide and the tourmaline nanoparticles, some new peaks appear in a Fourier transform infrared spectrogram of the graphene oxide aerogel, and a large number of characteristic absorption peaks exist in a GO spectrogram, wherein the characteristic absorption peaks are 3374cm^-1The absorption peak is the stretching vibration peak of-OH; 1224cm^-1A stretching vibration peak at an epoxy group (C-O-C), and 1059cm^-1The peak is the stretching vibration peak of the alkoxy (C-O). According to the spectrogram of the graphene oxide aerogel, the graphene oxide aerogel appears in a 1732cm spectrum relative to the GO spectrum^-1The absorption peak is the stretching vibration peak of carbonyl C ═ O, 165 ℃ m^-1The absorption peak at is-NH₂Stretching vibration peak to demonstrate a large number of carbonyl and amino groups on modified cotton fibers in graphene oxide aerogel and at 982cm^-1Characteristic peaks of Si-O groups appear at the positions, thereby indirectly proving the existence of the nano tourmaline.

As shown in fig. 3, broad spectrum testing of graphene oxide aerogel found that the N1s peaks were located at 399.77eV and 399.79eV, respectively, corresponding to the N1s peak at 399.74 in modified cotton fiber, indicating that the modified cotton fiber was successfully complexed with graphene oxide. In addition, an XPS spectrum of the tourmaline has an Si2p peak value, and an XPS spectrum of the graphene oxide aerogel has a Si2p peak value at 101.66eV, so that the existence of tourmaline nano particles is proved, energy spectrum peaks of sea oil, B3+ (193eV) and B0(188eV) in the XPS spectrum of the tourmaline, photoelectron peaks of Al2p1 and Al2p3 at 72-77 eV and photoelectron peaks of Fe2p3 at 706eV are proved that the graphene oxide aerogel is compounded with the tourmaline nano particles.

Preparation of electrothermal fabric

The electric heat fabric that this application embodiment provided has the fire prevention outer layer that stacks gradually the setting, graphite oxide aerogel layer and waterproof inlayer, wherein, graphite oxide aerogel layer adopts the preparation of the graphite oxide aerogel piece that above-mentioned embodiment (embodiment 1-13 and comparative example 1-12) prepared, through weaving the central point between fire prevention outer layer and waterproof inlayer and put different thickness graphite oxide graphene aerogel pieces, the cross string bag of weaving with aramid fiber line fixes graphite oxide graphene aerogel piece between waterproof inlayer and fire prevention outer layer, prevent that the displacement from appearing in the graphite oxide aerogel piece of compound surface fabric in the friction motion process.

Wherein, regarding the form of sewing of graphite oxide aerogel piece, can be specifically for the interval is sewed up, and the edge of four angles of graphite oxide aerogel piece is fixed between fire prevention outer layer and waterproof inlayer.

The preferable graphene oxide aerogel block is sewn in a manner that the graphene oxide aerogel block has a sewn edge portion, the edge portion of each graphene oxide aerogel block and the other edge of the other graphene oxide aerogel block are not mutually spliced and then are laminated into a whole, the thickness of the laminated graphene oxide aerogel block is equal to the thickness of the other parts of the graphene oxide aerogel block except the edge portion, and thus, the graphene oxide aerogel block is spliced together through the edge portions and then sewn on the spliced edge portions, so that the graphene oxide aerogel layer of the whole non-vacant part is formed, and a completely closed graphene oxide aerogel layer is formed.

The graphene oxide aerogel block can be cut into a film with the thickness of about 0.25-0.54 mm, the planar shape is not limited, and the film can be in any shape, such as a rectangle, a square, a circle, a regular polygon or an irregular shape, and the thickness of the graphene oxide aerogel block is half of the thickness of the central main body part of the graphene oxide aerogel block, so that related splicing and sewing are facilitated.

Wherein the fireproof outer layer is prepared from 98 wt% of aramid 1313 and 2 wt% of aramid 1414, and the areal density is 193.7g/cm²And the thickness is 0.32 mm. The waterproof inner layer is formed by needling 100 wt% of aramid 1313 felt and base cloth, and has an areal density of 200g/cm²And the thickness is 0.41 mm.

Analysis of electrothermal Fabric Properties

1. Basic electrothermal performance test

The electrothermal fabrics prepared in each of examples 1 to 13 and comparative examples 1 to 12 were cut into 10mm × 45mm samples, and then both ends of the 45mm long side of the sample were connected in series with a 10V external dc power supply for 120 seconds and then disconnected, and the surface temperature of the electrothermal fabric was recorded by a thermal infrared imager (shanghai spectral union, optoelectronics and technology co., ltd). The time for the temperature of the electric heating fabric to rapidly rise to a relatively stable temperature within 120s and to rapidly rise to a relatively stable temperature by 80% after slowly reaching the highest temperature is defined as the electric heating response time of the electric heating fabric.

As shown in Table 3, the electrothermal response time of the electrothermal fabrics prepared in examples 1 to 13 was not higher than 30s, while the electrothermal response time of the electrothermal fabrics prepared in comparative examples 1 to 12 was higher than 30 s. In addition, the stable maximum temperature of the electric heating fabrics prepared in examples 1 to 13 is more than 80 ℃, while the stable maximum temperature of the electric heating fabrics prepared in comparative examples 1 to 12 is not more than 75 ℃, and the electric heating effect is inferior to that of the electric heating fabrics prepared in examples 1 to 13. Therefore, the electric heating fabric provided by the embodiment of the application has more excellent electric heating effect.

TABLE 3 Performance of electrothermal fabrics

In order to further characterize the stability of the electrothermal performance of the electrothermal fabrics prepared in each of examples 1 to 13 and comparative examples 10 to 12, different continuous stabilizing voltages were applied to each of the above-mentioned 10mm × 45mm samples for 120s, followed by cooling off, recording the power of the electrothermal fabric during the voltage increase from 4V to 12V, and calculating the power density from the area of the sample. As can be seen from Table 3, the maximum power densities of the electrothermal fabrics prepared in examples 1 to 13 are all significantly lower than those of comparative examples 1 to 12, which indicates that the electrothermal fabrics have lower energy consumption and higher electric conduction effect when exerting the electrothermal function.

In order to further explore the primary application of the composite fabric, the 10mm × 45mm samples are fixed on the back of the hand, the center point of the sample and the back of the hand with the edge of 2cm are respectively connected with the positive electrode and the negative electrode of a 6V direct current power supply, and the temperature of the back of the hand with the edge of 2cm is recorded by an infrared thermal imager.

TABLE 4 hand electrothermal effect of electrothermal fabric

The maximum temperature reached by the skin on the back of the hand 2cm from the edge of the sample, the time taken to reach the maximum temperature, and the time taken to return to the normal temperature after the temperature on the back of the hand was turned off (cooling time in Table 3) are shown in Table 4, respectively. As shown in Table 4, the skin temperature of the back of the hand with 2cm edge of the sample can reach 40 ℃ within about 8-12 min, which indicates that the temperature rise speed of the composite fabric heater is high and the voltage is safe.

Among them, the electric heating fabrics prepared in examples 1 to 13 all reached the highest temperature for a significantly lower time than those of comparative examples 1 to 12, and the highest temperatures reached therewith were all significantly higher than those of comparative examples 1 to 12, thereby illustrating that the electric heating fabrics prepared in examples 1 to 13 can induce the temperature rise of the skin on the back of the hand more rapidly and can reach higher temperatures. Moreover, the time for the electric heating fabrics prepared in examples 1-13 to return to normal temperature after the skin temperature of the back of the hand is significantly higher than that of comparative examples 1-12 after power failure, which shows that the electric heating fabrics prepared in examples 1-13 have more durable electric heating effect on the back of the hand.

The analysis of the results in tables 1-4 shows that:

1) the difference of exerting the main electrothermal performance of electrothermal fabric that this application embodiment provided lies in oxidation graphite alkene aerogel layer, and in the preparation process of this application oxidation graphite alkene aerogel, the factor of deciding its oxidation graphite alkene aerogel performance mainly has the concentration of oxidation graphite alkene solution, the modified cotton fiber concentration that contains in the oxidation graphite alkene solution, the concentration of nanometer tourmaline solution, oxidation graphite alkene solution and nanometer tourmaline solution volume ratio and the air volume in step 2).

2) The difference between examples 1 to 3 and comparative examples 1 to 2 is mainly that the modified cotton fibers are different during the preparation of the graphene oxide aerogel, and the maximum power density and the time for the back of the hand to return to the normal temperature after the power is turned off in the corresponding electrothermal performance of the electrothermal fabric are significantly changed, which indicates that the mechanical properties of the modified cotton fibers in the graphene oxide aerogel are changed, and the energy loss of the final electrothermal fabric and the performance of the continuous electrothermal action of the final electrothermal fabric are affected.

3) The difference between examples 4-5 and comparative examples 3-4 lies in the difference in the concentration of the graphene oxide solution during the preparation of the graphene oxide aerogel, and thus the corresponding electrothermal time of the electrothermal fabric is determined, the maximum temperature, the maximum power density and the significant difference in the electrothermal performance of the hand back are reached, which shows that the concentration of graphene oxide in the graphene oxide aerogel has a significant influence on the electrothermal performance and the practical application performance of the final electrothermal fabric.

4) Examples 6 to 7 are different from comparative examples 5 to 6 in the concentration of modified cotton fibers in the graphene oxide solution during the preparation of the graphene oxide aerogel. Examples 8 to 9 are different from comparative examples 7 to 8 in the concentration of the nano tourmaline solution during the preparation of the graphene oxide aerogel. Examples 10 to 11 are different from comparative examples 9 to 10 in the volume ratio of the graphene oxide solution to the nano tourmaline solution during the preparation of the graphene oxide aerogel. Examples 12 to 13 are different from comparative examples 11 to 12 in the difference in the ventilation amount in step 2) in the graphene oxide aerogel preparation process. These factors all contribute to the corresponding time of electric heating of the final electric heating fabric, the maximum temperature reached, the maximum power density and the significant difference of the electric heating performance of the hand back, thereby illustrating the importance of these factors in the preparation process of the graphene oxide aerogel of the embodiment of the present application. It is based on these considerations that the present inventors have completed the present invention.

In addition, in the structure of the electric heating fabric, the fireproof outer layer and the waterproof inner layer are introduced, so that the electric heating fabric can also play a fireproof function and a waterproof function when playing an electric heating function, and higher safety is provided for the application of the electric heating fabric as wearable equipment.

The above description is only for the preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application.