Graphene glass fiber electric heating cloth and electric heating composite cloth

Abstract

The application relates to the technical field of graphene composite materials, in particular to a graphene glass fiber electric heating cloth and an electric heating composite cloth. The graphene glass fiber electric heating cloth is prepared by the following steps: after the glass fiber cloth is ultrasonically cleaned and dried, a pre-deposited glass fiber cloth is obtained by chemical vapor deposition through mixed gas a and mixed gas b in sequence; epoxy resin, tourmaline powder, nano titanium dioxide, lanthanum nitrate and a dispersing agent are added into water and ball milled, a curing agent is added and ultrasonically treated, and the pre-deposited glass fiber cloth is coated on the surface and heat-treated at 105-115 DEG C for more than 2 hours in an argon atmosphere containing water vapor. The electric heating composite cloth comprises, from top to bottom, a flexible fabric base body, an insulating protective layer, the graphene glass fiber electric heating cloth, an electrode sheet, an insulating protective layer and a flexible fabric base body, and the layers are connected through heat-conducting glue. The obtained electric heating composite cloth can emit far infrared rays and has strong permeability.

Description

Technical Field

[0001] This invention relates to the field of graphene composite materials technology, and in particular to a graphene glass fiber electric heating cloth and an electric heating composite cloth. Background Technology

[0002] Far-infrared radiation heating materials have become a research hotspot in the medical and health field, particularly in the physiotherapy applications for diseases such as rheumatism, joint strain, and dysmenorrhea in women. While graphene heating films, as the current mainstream flexible heating material, have shown certain therapeutic effects, a series of significant technical bottlenecks still exist in practical applications, severely limiting their performance and application scope.

[0003] Existing products mostly use engineering plastics such as PET and PI as carrier materials. Although these materials have good insulation, flame retardancy, and high temperature resistance, they exhibit significant limitations in actual use (especially in high-frequency bending scenarios such as joint movements). When the material is repeatedly bent, it is prone to uneven heating due to excessive bending, and may even cause skin damage due to the sharp edges of the material. This lack of mechanical properties directly affects the comfort and safety of the product, limiting its application in parts of the human body that require frequent bending.

[0004] Supergraphene materials, as an emerging member of the graphene composite family, form continuous graphene layers through high-temperature chemical deposition on traditional engineering materials. This avoids the challenging peeling-transfer process and solves the problem of non-self-support in ultrathin graphene films. Supergraphene fiberglass cloth is one type of supergraphene material, which deposits continuous graphene films on the surface of traditional materials through a high-temperature growth process and ingenious process design. By leveraging high-performance graphene "skin," traditional materials are endowed with entirely new functions, allowing atomically thin graphene films to enter the market on traditional material carriers.

[0005] However, graphene-based far-infrared heating materials have significant drawbacks in energy conversion efficiency, with generally low radiative temperature rise efficiency, making it difficult to achieve a sustained and stable heating effect. Simultaneously, the material's insufficient far-infrared emissivity results in limited energy penetration depth, failing to effectively act on deep tissues. This low energy conversion efficiency not only affects the therapeutic effect but also increases energy consumption, reducing the product's practicality and cost-effectiveness.

[0006] More importantly, the heating performance of existing materials deteriorates significantly during long-term use. This performance degradation is directly related to the mechanical fatigue of the carrier material and the structural stability of the graphene layers. Specifically, repeated bending causes microcracks to form between the graphene layers and gradually propagate, destroying the original conductive network structure. Simultaneously, the substrate is prone to deformation in humid and hot environments, which further exacerbates the deterioration of material performance. Long-term performance instability severely impacts the product's lifespan and reliability. Summary of the Invention

[0007] The purpose of this invention is to address the shortcomings of existing technologies by proposing a graphene glass fiber electric heating cloth and an electric heating composite cloth.

[0008] A graphene glass fiber electric heating cloth is prepared by the following steps:

[0009] (1) After ultrasonic cleaning of the glass fiber cloth, it is dried and then chemical vapor deposition is carried out in sequence using mixed gas a and mixed gas b to obtain pre-deposited glass fiber cloth.

[0010] Mixed gas a includes: argon, ethanol vapor, hydrogen, and ammonia. The flow rate ratio of argon, ethanol vapor, hydrogen, and ammonia is 800-1200:120-140:120-140:50-100 (unit: sccm).

[0011] The mixed gas b includes: diborane and ammonia, with a flow rate ratio of 20-40:50-100 (unit: sccm);

[0012] (2) Add epoxy resin, tourmaline powder, nano titanium dioxide, lanthanum nitrate and dispersant to water and ball mill for 1-2 hours. Add curing agent and ultrasonically treat for 10-30 minutes. Coat the surface of pre-deposited glass fiber cloth and heat treat at 105-115℃ for more than 2 hours in an argon atmosphere containing water vapor.

[0013] Preferably, the glass fiber cloth has a plain weave and a warp and weft density of 12-18 × 12-18 threads / cm. 2 The yarn fineness is 32tex, and the thickness of the fiber cloth is 0.05-0.1mm.

[0014] Preferably, the flow rate of ammonia in the mixed gas a is 50-100 sccm.

[0015] Preferably, the flow rate of ammonia in the mixed gas b is 50-100 sccm.

[0016] Preferably, the glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and then deionized water.

[0017] Preferably, the specific operation of chemical vapor deposition is as follows: the ultrasonically cleaned and dried glass fiber cloth is sent into the CVD furnace, purged with argon for 10-20 min, heated to 750-800℃, held for 10-20 min, heated to 1150-1200℃, mixed gas a is introduced, held for 1-2 h, cooled to 1000-1050℃, mixed gas b is introduced, held for 10-30 min, helium is introduced, and the mixture is allowed to cool naturally to room temperature.

[0018] More preferably, during the process of heating to 750-800℃, the heating rate is 5-10℃ / min.

[0019] More preferably, during the process of heating to 1150-1200℃, the heating rate is 2-3℃ / min.

[0020] Preferably, the mass ratio of epoxy resin, tourmaline powder, nano titanium dioxide, lanthanum nitrate, dispersant, and curing agent is 10-20:1-3:1-2:0.01-0.1:0.1-0.5:5-10.

[0021] Preferably, the dispersant is sodium dodecylbenzenesulfonate.

[0022] Preferably, the curing agent is a polyamide-based curing agent.

[0023] Preferably, in the argon atmosphere containing water vapor, the volume fraction of water vapor is 1-2%.

[0024] An electric heating composite cloth comprises, from top to bottom: a flexible fabric substrate, an insulating protective layer, the aforementioned graphene glass fiber electric heating cloth, an electrode sheet, an insulating protective layer, and a flexible fabric substrate, with each layer bonded together by a thermally conductive adhesive.

[0025] Preferably, the flexible fabric matrix is ​​a polyester fiber fabric.

[0026] Preferably, the insulating protective layer is a polyimide film.

[0027] Beneficial effects:

[0028] In this invention, during the CVD process, a hexagonal boron nitride protective layer is grown by introducing a mixed gas of diborane and ammonia after graphene growth. The layered structure of hexagonal boron nitride has a low lattice mismatch with graphene, and the layers form a tight heterojunction interface through van der Waals forces, significantly improving the interlayer bonding energy. Specifically, the hexagonal boron nitride layer not only effectively inhibits the propagation of microcracks between graphene layers, but also uniformly disperses stress during bending, preventing stress concentration and damage to the conductive network. Furthermore, the high thermal conductivity of the hexagonal boron nitride layer facilitates heat conduction, while its chemical inertness blocks water and oxygen permeation, significantly reducing the deformation rate under humid and hot conditions and preventing material degradation caused by localized overheating.

[0029] During the heat treatment process of this invention, in an argon atmosphere containing water vapor, the tourmaline powder in the epoxy resin-based coating releases far-infrared rays through dipole vibration due to the asymmetry of its crystal structure when the temperature changes. At the same time, the rare earth element lanthanum doped titanium dioxide can introduce defects such as oxygen vacancies on the particle surface, increasing the polarizability of the material and forming a composite structure with tourmaline to further enhance far-infrared radiation. The combined effect significantly improves the far-infrared emissivity of the material.

[0030] This invention effectively blocks water and oxygen penetration through the high chemical inertness and dense structure of the hexagonal boron nitride layer, inhibiting the propagation of microcracks between graphene layers and the destruction of the conductive network. Meanwhile, the photostabilizing effect of titanium dioxide and the synergistic effect of lanthanum ions in the epoxy resin-based coating slow down the hydrolysis and cross-linking structure destruction of the epoxy resin. Combined with the high thermal conductivity of the hexagonal boron nitride layer to accelerate heat diffusion and avoid local overheating, this invention significantly improves the long-term stability of the material in humid and hot environments.

[0031] The electrically heated composite fabric obtained by this invention emits far-infrared rays when heated by electricity. It has strong penetrating power, which can promote local blood circulation and may help relieve joint discomfort symptoms and assist in the treatment of local areas. Attached Figure Description

[0032] Figure 1 The graph shows a comparison of the far-infrared radiation temperature rise and far-infrared emissivity of the electric heating composite fabric made from the graphene glass fiber electric heating fabric obtained in Examples 1-5.

[0033] Figure 2 The graph shows a comparison of the heating rise value, the difference between the maximum heating rise value and the minimum heating rise value of the electric heating composite cloth made from the graphene glass fiber electric heating cloth obtained in Examples 1-5 after applying a voltage of 30V for 1 minute.

[0034] Figure 3 The graph shows a comparison of the heating temperature rise, the difference between the maximum heating temperature rise and the minimum heating temperature rise after applying a 30V voltage for 1 minute to the electric heating composite cloth made from the graphene glass fiber electric heating cloth obtained in Examples 1-5 after folding 180° 5 times. Detailed Implementation

[0035] The present invention will be further explained below with reference to specific embodiments.

[0036] The fiberglass cloth used below is a plain weave fabric formed by weaving fiberglass, with 16×16 fibers / cm. 2 32 tex, thickness 0.08±0.01 mm. The nano titanium dioxide used below is rutile type, with a particle size of 20-50 nm. The tourmaline powder used below is 200 mesh.

[0037] Example 1

[0038] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0039] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 10 min. The temperature is increased to 750℃ at a rate of 5℃ / min and held for 10 min. The temperature is then increased to 1150℃ at a rate of 2℃ / min. Mixed gas a (composed of 800 sccm of argon gas, 120 sccm of ethanol vapor, 120 sccm of hydrogen gas, and 50 sccm of ammonia gas) is introduced and held for 1 h. The temperature is then reduced to 1000℃ and mixed gas b (composed of 20 sccm of diborane gas and 50 sccm of ammonia gas) is introduced and held for 10 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0040] S2. Add 10g of epoxy resin E-44, 1g of tourmaline powder, 1g of nano titanium dioxide, 0.01g of lanthanum nitrate, and 0.1g of sodium dodecylbenzene sulfonate to 30g of deionized water and mechanically ball-mill for 1h at a ball-milling speed of 400r / min. Add 5g of polyamide 650 curing agent and ultrasonically treat at a frequency of 60kHz for 10min. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 105℃ for 2h in an argon atmosphere containing water vapor (volume fraction of 1%), and then cool to room temperature.

[0041] Example 2

[0042] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0043] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 20 min. The temperature is increased to 800℃ at a rate of 10℃ / min and held for 20 min. The temperature is then increased to 1200℃ at a rate of 3℃ / min. Mixed gas a (composed of 1200 sccm of argon gas, 140 sccm of ethanol vapor, 140 sccm of hydrogen gas, and 100 sccm of ammonia gas) is introduced and held for 2 h. The temperature is then reduced to 1050℃ and mixed gas b (composed of 40 sccm of diborane gas and 100 sccm of ammonia gas) is introduced and held for 30 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0044] S2. Add 20g of epoxy resin E-44, 3g of tourmaline powder, 2g of nano titanium dioxide, 0.1g of lanthanum nitrate, and 0.5g of sodium dodecylbenzene sulfonate to 40g of deionized water and mechanically ball-mill for 2 hours at a ball-milling speed of 600r / min. Add 10g of polyamide 650 curing agent and ultrasonically treat at a frequency of 90kHz for 30 minutes. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 115℃ for 4 hours in an argon atmosphere containing water vapor (volume fraction of 2%), and then cool to room temperature.

[0045] Example 3

[0046] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0047] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 12 min. The temperature is increased to 770℃ at a rate of 9℃ / min and held for 18 min. The temperature is then increased to 1170℃ at a rate of 2.5℃ / min. Mixed gas a (composed of 1100 sccm of argon gas, 125 sccm of ethanol vapor, 135 sccm of hydrogen gas, and 70 sccm of ammonia gas) is introduced and held for 100 min. The temperature is then reduced to 1020℃ and mixed gas b (composed of 35 sccm of diborane gas and 70 sccm of ammonia gas) is introduced and held for 25 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0048] S2. Add 12g of epoxy resin E-44, 2.5g of tourmaline powder, 1.3g of nano titanium dioxide, 0.08g of lanthanum nitrate, and 0.2g of sodium dodecylbenzene sulfonate to 38g of deionized water and mechanically ball-mill for 80min at a ball-milling speed of 550r / min. Add 6g of polyamide 650 curing agent and ultrasonically treat at a frequency of 70kHz for 25min. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 108℃ for 3.5h in an argon atmosphere containing water vapor (volume fraction of 1.5%), and then cool to room temperature.

[0049] Example 4

[0050] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0051] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 18 min. The temperature is increased to 790℃ at a rate of 7℃ / min and held for 12 min. The temperature is then increased to 1190℃ at a rate of 2.5℃ / min. Mixed gas a (composed of 900 sccm of argon gas, 135 sccm of ethanol vapor, 125 sccm of hydrogen gas, and 90 sccm of ammonia gas) is introduced and held for 80 min. The temperature is then reduced to 1020℃ and mixed gas b (composed of 25 sccm of diborane gas and 90 sccm of ammonia gas) is introduced and held for 15 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0052] S2. Add 18g of epoxy resin E-44, 1.5g of tourmaline powder, 1.7g of nano titanium dioxide, 0.02g of lanthanum nitrate, and 0.4g of sodium dodecylbenzene sulfonate to 32g of deionized water and mechanically ball-mill for 100min at a ball-milling speed of 450r / min. Add 9g of polyamide 650 curing agent and ultrasonically treat at a frequency of 80kHz for 15min. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 112℃ for 2.5h in an argon atmosphere containing water vapor (volume fraction of 1.5%), and then cool to room temperature.

[0053] Example 5

[0054] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0055] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 15 min. The temperature is increased to 780℃ at a rate of 8℃ / min and held for 15 min. The temperature is then increased to 1180℃ at a rate of 2.5℃ / min. Mixed gas a (composed of 1000 sccm of argon gas, 130 sccm of ethanol vapor, 130 sccm of hydrogen gas, and 80 sccm of ammonia gas) is introduced and held for 90 min. The temperature is then reduced to 1020℃ and mixed gas b (composed of 30 sccm of diborane gas and 80 sccm of ammonia gas) is introduced and held for 20 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0056] S2. Add 15g of epoxy resin E-44, 2g of tourmaline powder, 1.5g of nano titanium dioxide, 0.05g of lanthanum nitrate, and 0.3g of sodium dodecylbenzene sulfonate to 35g of deionized water and mechanically ball-mill for 90min at a ball-milling speed of 500r / min. Add 7.5g of polyamide 650 curing agent and ultrasonically treat at a frequency of 75kHz for 20min. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 110℃ for 3h in an argon atmosphere containing water vapor (volume fraction of 1.5%), and then cool to room temperature.

[0057] Comparative Example 1

[0058] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0059] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 15 min. The temperature is increased to 780°C at a rate of 8°C / min and held for 15 min. The temperature is then increased to 1180°C at a rate of 2.5°C / min. Mixed gas a (composed of 1000 sccm of argon gas, 130 sccm of ethanol vapor, 130 sccm of hydrogen gas, and 80 sccm of ammonia gas) is introduced and held for 90 min. The temperature is then reduced to 1020°C and helium gas is introduced. The mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0060] S2. Add 15g of epoxy resin E-44, 2g of tourmaline powder, 1.5g of nano titanium dioxide, 0.05g of lanthanum nitrate, and 0.3g of sodium dodecylbenzene sulfonate to 35g of deionized water and mechanically ball-mill for 90min at a ball-milling speed of 500r / min. Add 7.5g of polyamide 650 curing agent and ultrasonically treat at a frequency of 75kHz for 20min. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 110℃ for 3h in an argon atmosphere containing water vapor (volume fraction of 1.5%), and then cool to room temperature.

[0061] Comparative Example 2

[0062] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0063] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 15 min. The temperature is increased to 780℃ at a rate of 8℃ / min and held for 15 min. The temperature is then increased to 1180℃ at a rate of 2.5℃ / min. Mixed gas a (composed of 1000 sccm of argon gas, 130 sccm of ethanol vapor, 130 sccm of hydrogen gas, and 80 sccm of ammonia gas) is introduced and held for 90 min. The temperature is then reduced to 1020℃ and mixed gas b (composed of 30 sccm of diborane gas and 80 sccm of ammonia gas) is introduced and held for 20 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0064] S2. Add 15g of epoxy resin E-44, 2g of tourmaline powder, 1.55g of nano titanium dioxide, and 0.3g of sodium dodecylbenzene sulfonate to 35g of deionized water and mechanically ball-mill for 90min at a ball-milling speed of 500r / min. Add 7.5g of polyamide 650 curing agent and ultrasonically treat at a frequency of 75kHz for 20min. Coat the surface of the pre-deposited glass fiber cloth. Heat treat at 110℃ for 15min in an argon atmosphere containing water vapor (volume fraction of 1.5%), and then cool to room temperature.

[0065] Comparative Example 3

[0066] A method for preparing a graphene glass fiber electric heating cloth includes the following steps:

[0067] S1. The glass fiber cloth is ultrasonically cleaned sequentially with deionized water, ethanol, and deionized water, and then dried with argon gas. It is then placed in a CVD furnace and purged with 500 sccm of argon gas for 15 min. The temperature is increased to 780℃ at a rate of 8℃ / min and held for 15 min. The temperature is then increased to 1180℃ at a rate of 2.5℃ / min. Mixed gas a (composed of 1000 sccm of argon gas, 130 sccm of ethanol vapor, 130 sccm of hydrogen gas, and 80 sccm of ammonia gas) is introduced and held for 90 min. The temperature is then reduced to 1020℃ and mixed gas b (composed of 30 sccm of diborane gas and 80 sccm of ammonia gas) is introduced and held for 20 min. Helium gas is then introduced and the mixture is allowed to cool naturally to room temperature to obtain the pre-deposited glass fiber cloth.

[0068] S2. Add 15g of epoxy resin E-44, 2g of tourmaline powder, 1.5g of nano titanium dioxide, 0.05g of lanthanum nitrate, and 0.3g of sodium dodecylbenzene sulfonate to 35g of deionized water and mechanically ball-mill for 90min at a ball-milling speed of 500r / min. Add 7.5g of polyamide 650 curing agent and ultrasonically treat at a frequency of 75kHz for 20min. Coat the surface of the pre-deposited glass fiber cloth. Heat-treat at 110℃ for 3h in an argon atmosphere and then cool to room temperature.

[0069] Electrically heated composite fabrics (20cm × 20cm) were prepared using the graphene glass fiber electrically heated fabrics obtained in Examples 1-5 and Comparative Examples 1-3, respectively. Each group of electrically heated composite fabrics, from top to bottom, comprises: polyester fiber fabric (from a textile company in Jinjiang, 50D polyester network yarn, 1+1 rib knitted fabric), polyimide film (DuPont, thickness 15±3μm), the aforementioned graphene glass fiber electrically heated fabric, copper foil, polyimide film (DuPont, thickness 15±3μm), and polyester fiber fabric (from a textile company in Jinjiang, 50D polyester network yarn, 1+1 rib knitted fabric). The layers are bonded together using thermally conductive adhesive (3M, model TC2810).

[0070] The far-infrared properties of each group of electrically heated composite fabrics were measured using a textile far-infrared emissivity tester and a textile far-infrared radiation temperature rise tester, in accordance with GB / T 30127-2013 "Test and Evaluation of Far-Infrared Properties of Textiles".

[0071] like Figure 1 As shown, the far-infrared radiation heating value and far-infrared emissivity of the electric heating composite fabric made from the graphene glass fiber electric heating cloth obtained in Examples 1-5 are significantly higher than those of Comparative Examples 1-3, confirming that the far-infrared performance of the electric heating composite fabric obtained in this invention is the best; while the far-infrared radiation heating value and far-infrared emissivity of the electric heating composite fabric made from the graphene glass fiber electric heating cloth obtained in Example 5 are the highest.

[0072] The copper foil in each group of electrically heated composite cloths was soldered to the wires. A voltage of 30V was applied to each group of electrically heated composite cloths for 1 minute. Five points were selected on the surface of the electrically heated composite cloths, and the heating temperature rise value on the surface of the electrically heated composite cloths was measured using an infrared thermometer. The difference between the maximum heating temperature rise value and the minimum heating temperature rise value was calculated.

[0073] like Figure 2 As shown, the heating value of the electric heating composite cloth made from the graphene glass fiber electric heating cloth obtained in Examples 1-5 is significantly higher than that of Comparative Examples 1-3, while the difference between the maximum heating value and the minimum heating value is significantly smaller than that of Comparative Examples 1-3. At the same time, the heating value of the electric heating composite cloth made from the graphene glass fiber electric heating cloth obtained in Example 5 is the largest, while the difference between the maximum heating value and the minimum heating value is the smallest.

[0074] The graphene glass fiber electric heating cloths obtained in Examples 1-5 and Comparative Examples 1-3 were folded 180° five times. The electric heating composite cloths were then prepared again according to the above-described method. Wires were then welded, and a voltage of 30V was applied to each group of electric heating composite cloths for 1 minute. Five points were selected on the surface of the electric heating composite cloths, and the heating temperature rise value was measured using an infrared thermometer. The difference between the maximum and minimum heating temperature rise values ​​was calculated. These values ​​were compared with the heating temperature rise values ​​of each group when folded and the difference between the maximum and minimum heating temperature rise values. The retention rate of the heating temperature rise value and the growth rate of the maximum and minimum temperature difference after folding were calculated for each group.

[0075] Heat rise retention rate = heat rise after 5 folds ÷ heat rise when not folded × 100%.

[0076] Maximum and minimum temperature difference growth rate = (difference between maximum and minimum heat rise after 5 folds - difference between maximum and minimum heat rise when not folded) ÷ difference between maximum and minimum heat rise when not folded × 100%.

[0077] like Figure 3 As shown, the heat rise retention rate of the electric heating composite cloth made from the graphene glass fiber electric heating cloth obtained in Examples 1-5 after folding is significantly higher than that of Comparative Examples 1-3, while the maximum and minimum temperature difference growth rate is significantly lower than that of Comparative Examples 1-3. At the same time, the heat rise retention rate of the electric heating composite cloth made from the graphene glass fiber electric heating cloth obtained in Example 5 after folding is the largest, while the maximum and minimum temperature difference growth rate is the smallest.

[0078] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A graphene glass fiber electric heating cloth, characterized in that, The graphene glass fiber electric heating cloth is prepared using the following steps: (1) After ultrasonic cleaning of the glass fiber cloth, it is dried and then chemical vapor deposition is carried out in sequence using mixed gas a and mixed gas b to obtain pre-deposited glass fiber cloth. The mixed gas a includes: argon, ethanol vapor, hydrogen, and ammonia, with the flow rate ratio of argon, ethanol vapor, hydrogen, and ammonia being 800-1200:120-140:120-140:50-100. The mixed gas b includes: diborane and ammonia, with a flow rate ratio of 20-40:50-100 for diborane and ammonia. (2) Add epoxy resin, tourmaline powder, nano titanium dioxide, lanthanum nitrate and dispersant to water and ball mill for 1-2 hours. Add curing agent and ultrasonically treat for 10-30 minutes. Coat the surface of pre-deposited glass fiber cloth and heat treat at 105-115℃ for more than 2 hours in an argon atmosphere containing water vapor.

2. The graphene glass fiber electric heating cloth according to claim 1, characterized in that, The fiberglass cloth has a plain weave structure with a warp and weft density of 12-18 × 12-18 threads / cm. 2 The yarn fineness is 32tex, and the thickness of the fiber cloth is 0.05-0.1mm.

3. The graphene glass fiber electric heating cloth according to claim 1, characterized in that, In gas mixture a, the flow rate of ammonia is 50-100 sccm; in gas mixture b, the flow rate of ammonia is 50-100 sccm.

4. The graphene glass fiber electric heating cloth according to claim 1, characterized in that, The fiberglass cloth was ultrasonically cleaned sequentially with deionized water, ethanol, and then deionized water.

5. The graphene glass fiber electric heating cloth according to claim 1, characterized in that, The specific operation of chemical vapor deposition is as follows: After ultrasonic cleaning and drying, the glass fiber cloth is placed into the CVD furnace, purged with argon for 10-20 minutes, heated to 750-800℃, held for 10-20 minutes, and then heated to 1150-1200℃. Mixed gas a is introduced and held for 1-2 hours. The temperature is then lowered to 1000-1050℃, mixed gas b is introduced and held for 10-30 minutes, helium is introduced, and the temperature is allowed to drop naturally to room temperature.

6. The graphene glass fiber electric heating cloth according to claim 5, characterized in that, During the process of heating to 750-800℃, the heating rate is 5-10℃ / min; During the process of heating to 1150-1200℃, the heating rate is 2-3℃ / min.

7. The graphene glass fiber electric heating cloth according to claim 1, characterized in that, The mass ratio of epoxy resin, tourmaline powder, nano titanium dioxide, lanthanum nitrate, dispersant, and curing agent is 10-20:1-3:1-2:0.01-0.1:0.1-0.5:5-10; The dispersant is sodium dodecylbenzenesulfonate.

8. The graphene glass fiber electric heating cloth according to claim 1, characterized in that, In an argon atmosphere containing water vapor, the volume fraction of water vapor is 1-2%.

9. An electrically heated composite fabric, characterized in that, From top to bottom, including: The flexible fabric substrate, the insulating protective layer, the graphene glass fiber electric heating cloth as described in any one of claims 1-8, the electrode sheet, the insulating protective layer, and the flexible fabric substrate are bonded together by thermally conductive adhesive.

10. The electrically heated composite fabric according to claim 9, characterized in that, The flexible fabric matrix is ​​made of polyester fiber fabric; the insulating protective layer is made of polyimide film.

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