CN115928279A - Graphene/silicone rubber coaxial fiber-based elastic core-spun yarn and preparation and application thereof - Google Patents
Graphene/silicone rubber coaxial fiber-based elastic core-spun yarn and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method and application of graphene/silicon rubber coaxial fiber-based elastic core-spun yarn, which is characterized by comprising the following steps: 1. preparing a graphene/silicone rubber mixed dispersion liquid by a high-speed shearing stripping method, and further preparing graphene/silicone rubber composite fibers by a solution spinning method; 2. preparing graphene/silicon rubber coaxial fibers by adopting a coaxial solution spinning method, wherein a core layer of the graphene/silicon rubber coaxial fibers is graphene/silicon rubber composite fibers, and a shell layer of the graphene/silicon rubber coaxial fibers is pure silicon rubber; 3. and preparing twisted pairs from the two fibers, and coating chemical fibers such as polyamide and the like by a blending method to prepare the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn. The graphene/silicon rubber coaxial fiber-based elastic core-spun yarn obtained by the invention has excellent elasticity, durability and stability, a single core-spun yarn can be used as a friction nano-generator, the integration level is high, the volume is small, the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn can be directly adhered to a human body or woven into a fabric, and the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn can be used as a self-powered sensor to effectively monitor the motion of the human body.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a graphene/silicon rubber coaxial fiber-based elastic core-spun yarn and a preparation method and application thereof.
Background
In recent years, the wide fields of electronic skin, wearable healthcare, biomedical monitors, smart clothing, artificial intelligence systems, and the like are vigorously developed, and the development of a new generation of flexible electronic devices, including high stretchability, high sensitivity, and good durability/stability, is urgently required. However, conventional rigid power systems such as rechargeable batteries are bulky, heavy, and limited in capacity, which presents serious challenges to their durability, portability, and safety. Therefore, it is necessary to develop next generation energy harvesters with shape adaptability, controllability and cost effectiveness as sustainable power sources to drive the development of self-sufficient flexible electronic devices. Triboelectric nano-generators (TENGs) are an effective energy harvesting technology because they can convert ambient mechanical energy into electrical energy through triboelectric and electrostatic inductive coupling.
Researchers use ethyl cellulose and polyamide 6 co-spinning to prepare a fiber fabric as a triboelectric anode material, mix a strong electronegativity conductive material MXene sheet into a polyvinylidene fluoride nano-fiber fabric as a triboelectric cathode material, use a copper foil as a current collector, assemble a sheet-shaped friction nano-generator, can collect energy of compression deformation, can be used as a self-powered sensor to monitor human body movement, but the friction nano-generator has poor stretching and bending performance and large volume and is not suitable for being used as a micro device. Recently, researchers embed a functionalized conductor with a novel structure into a stretchable elastomer to design a stretchable electrode and a shape-adaptive friction nano-generator, for example, silver nanowires are embedded into silicone rubber to develop an ultra-stretching nano-generator, which shows excellent durability and energy collection capability under extreme deformation conditions and has a wide application prospect in wearable electronic products, but the friction nano-generator also has the problems of high material cost, poor interface effect and the like.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a graphene/silicone rubber coaxial composite fiber having good elasticity, conductivity, durability, stability, and excellent output performance, and a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following scheme:
< preparation method >
The invention provides a preparation method of a graphene/silicon rubber coaxial fiber-based elastic core-spun yarn, which is characterized by comprising the following steps of:
step 1, mixing expanded graphite with a component A (raw rubber) of the two-component silicon rubber, then processing for 10-60 minutes by using a high-speed emulsifying machine, stripping the expanded graphite under the adhesion and high-speed shearing action of the raw rubber to form few-layer or even single-layer graphene, then adding a component B (catalyst) of the two-component silicon rubber, continuing to perform emulsification processing for 2-10 minutes, and vacuumizing to remove bubbles to obtain a graphene/two-component silicon rubber dispersion liquid;
step 2, filling the graphene/two-component silicon rubber dispersion liquid obtained in the step 1 into an injector, and injecting the dispersion liquid into hot methyl silicone oil through injection equipment to thermally cure the two-component silicon rubber into fibers to obtain graphene/silicon rubber composite fibers;
step 3, mixing the component A and the component B of the double-component silicone rubber, carrying out high-speed shearing emulsification treatment for 2-10 minutes, and vacuumizing to remove bubbles to obtain a pure double-component silicone rubber dispersion liquid;
step 4, preparing the graphene/silicon rubber coaxial fiber by adopting a coaxial solution spinning method: respectively taking the graphene/double-component silicon rubber dispersion liquid obtained in the step 1 as a core layer and the pure double-component silicon rubber dispersion liquid obtained in the step 3 as a shell layer, subpackaging the two different injectors, respectively connecting the injectors to an inner tube and an outer tube of a coaxial needle, then injecting the two dispersion liquids into hot methyl silicone oil through injection equipment, and performing thermocuring to obtain graphene/silicon rubber coaxial fibers, wherein the core layer is graphene/silicon rubber composite fibers, and the shell layer is pure silicon rubber;
and 5, mutually winding the graphene/silicon rubber composite fiber obtained in the step 2 and the graphene/silicon rubber coaxial fiber obtained in the step 4 to form an elastic twisted wire or a multi-twisted wire, and blending chemical fiber on the surface of the elastic twisted wire or the multi-twisted wire to obtain the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn.
In the step 1, the bicomponent silicone rubber mainly comprises one of methyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber and fluorine silicone rubber, the mass ratio of the component A to the component B is 20 to 1 to 5, and the mass ratio of the expanded graphite to the bicomponent silicone rubber is 1 to 100.
Wherein in the step 1, the shearing speed of the high-speed emulsifying machine is 5000-50000rpm.
In the step 2, the temperature of the hot methyl silicone oil is 100-200 ℃, the inner diameter of a syringe needle is 0.4-5 mm, the injection speed is 1-20cm/min, and the heat treatment time of the composite fiber is 5-20min.
In the step 4, the diameter of an inner tube of the coaxial needle is 0.4 to 4mm, the diameter of an outer tube of the coaxial needle is 0.8 to 5mm, and the diameter ratio of the inner tube to the outer tube is 1 to 4.
In the step 4, the injection speed range is 1 to 20cm/min, the injection speed ratio of the inner pipe to the outer pipe is (2) to (1 to 1).
Wherein, in the step 5, the blending is performed in a ring spinning machine or a rotor spinning machine, preferably a ring spinning machine.
Wherein, in the step 5, the chemical fiber includes, but is not limited to, ethyl cellulose fiber, polyester fiber, polyamide fiber, polyurethane fiber, polyacrylonitrile fiber.
< graphene/silicone rubber coaxial fiber-based elastic core-spun yarn friction nano-generator >
Further, the invention also provides the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn friction nano-generator prepared by the method and application thereof.
In some embodiments, the present application provides an elastic core spun yarn triboelectric nanogenerator comprising:
constructing an elastic core-spun yarn friction nano-generator by taking chemical fiber as a friction layer, taking graphene/silicon rubber composite fiber as a positive electrode and taking graphene/silicon rubber coaxial fiber as another friction layer and a negative electrode, and
the elastic core-spun yarn friction nano generator is attached to a human body or a fabric, is stretched in the movement process, and charges are generated by friction of chemical fibers and a silicon rubber layer and are respectively led out by two conductive graphene/silicon rubber fibers, so that the elastic core-spun yarn friction nano generator can be used as a self-powered sensor to effectively monitor the movement of the human body.
Action and Effect of the invention
Compared with the prior art, the invention has the following beneficial effects:
1. a single elastic core-spun yarn can be used as a friction nano generator, has high integration level and small volume, can be directly stuck on a human body or woven into a fabric, and can be used as a self-powered sensor to effectively monitor the motion of the human body.
2. The elastic core-spun yarn has high elasticity, can adapt to dynamic detection of extreme deformation or irregular movement as a friction nano generator, has ultrahigh sensitivity, can detect weak signals, has good durability and stability, and can bear continuous and high-frequency stimulation response.
Drawings
Fig. 1 is a schematic diagram of the preparation of the graphene/methyl vinyl silicone rubber coaxial fiber prepared in the first embodiment;
fig. 2 is a schematic structural diagram of a graphene/methyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn friction nanogenerator prepared in the first embodiment;
fig. 3 is a monitoring of the motion over the knee of the graphene/methyl vinyl silicone rubber coaxial fiber-based elastic core spun yarn triboelectric nanogenerator prepared in example one;
fig. 4 is an open circuit voltage monitoring of the graphene/methyl vinyl silicone rubber coaxial fiber-based elastic core spun yarn triboelectric nanogenerator prepared in example one at knee flexion.
Detailed Description
The following describes specific embodiments of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn, the preparation method and the application thereof in detail with reference to the accompanying drawings.
< example one >
In this embodiment, a graphene/methyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn is prepared and directly adhered to a human body (fingers and knees) to serve as a self-powered sensor for monitoring human body movement.
The preparation method comprises the following steps:
1. mixing 5g of expanded graphite with 90g of component A of methyl vinyl silicone rubber, then intermittently processing for 30 minutes by using a high-speed emulsifying machine at the rotating speed of 20000rpm, then adding 10g of component B of the two-component silicone rubber and continuing the emulsification processing for 5 minutes at 5000rpm to uniformly mix the components, and vacuumizing the obtained graphene/methyl vinyl silicone rubber dispersion to remove bubbles;
2. preparing graphene/methyl vinyl silicone rubber composite fiber by adopting a solution spinning method, wherein the inner diameter of a syringe needle is 0.6mm, the injection speed is 5cm/min, the temperature of methyl silicone oil is 150 ℃, and the heat treatment time of the fiber is 10min;
3. mixing the component A and the component B of the methyl vinyl silicone rubber, emulsifying for 5 minutes at 5000rpm, and vacuumizing to remove bubbles to obtain a pure methyl vinyl silicone rubber dispersion liquid;
4. preparing graphene/methyl vinyl silicone rubber coaxial fibers by adopting a coaxial solution spinning method, respectively taking graphene/methyl vinyl silicone rubber dispersion as core liquid, pure methyl vinyl silicone rubber dispersion as shell liquid, taking methyl silicone oil at 150 ℃ as a coagulating bath, and adopting a coaxial needle with an inner tube diameter of 0.5mm, an outer tube diameter of 0.8mm, a core liquid injection speed of 5cm/min and a shell liquid injection speed of 2cm/min;
5. and mutually winding the graphene/methyl vinyl silicone rubber composite fiber and the graphene/methyl vinyl silicone rubber coaxial fiber to form an elastic twisted pair, and blending nylon 6 fiber on the surface of the elastic twisted pair through a ring spinning machine to obtain the graphene/methyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn.
And (3) performance characterization:
the preparation schematic diagram of the graphene/methyl vinyl silicone rubber coaxial fiber is shown in figure 1, the coaxial fiber has good elasticity, the breaking elongation of the coaxial fiber reaches 550%, and after the coaxial fiber is repeatedly stretched for 1000 times under 400% elongation, the structure and the tensile strength of the coaxial fiber are kept stable, which shows that the coaxial fiber has good durability and stability. In addition, the outer layer of the graphene/methyl vinyl silicone rubber coaxial fiber is non-conductive, the inner layer is conductive, and the conductivity of the inner graphene/methyl vinyl silicone rubber composite fiber reaches 2S/cm, so that the graphene/methyl vinyl silicone rubber coaxial fiber can be used as a current collector and an electrode.
The structural schematic diagram of the graphene/methyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn is shown in the attached figure 2, wherein a nylon 6 fiber coating layer is used as a friction layer, graphene/methyl vinyl silicone rubber composite fibers in contact with the friction layer have good conductivity and can be used as a positive electrode, pure methyl vinyl silicone rubber on the outer layer of the graphene/methyl vinyl silicone rubber coaxial fiber is used as another friction layer, and graphene/methyl vinyl silicone rubber composite fibers on the inner layer are used as a negative electrode, so that the elastic core-spun yarn friction nano-generator is constructed.
The elastic core-spun yarn friction nanometer generator is attached to fingers, knees or sewn on a wrist belt, the elastic core-spun yarn is stretched in the movement process, and the nylon 6 fiber coating layer and the methyl vinyl silicone rubber layer rub to generate positive and negative charges and voltage difference, so that the elastic core-spun yarn friction nanometer generator can be used as a self-powered sensor to effectively monitor the movement of a human body. Fig. 3 shows the elastic core-spun yarn nano-generator attached to the knee for exercise monitoring, fig. 4 is a performance curve of the elastic core-spun yarn nano-generator, the maximum open circuit voltage of which is 180V, the short circuit current of which is 1.3 mua, and the output power of which is 470 muw, which are enough to power wearable electronic equipment.
< example II >
In the second embodiment, the graphene/methyl phenyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn is prepared and woven on wristbands and gloves to serve as a self-powered sensor to monitor human body movement.
The preparation method comprises the following steps:
1. mixing 4g of expanded graphite with 95g of the component A of the methyl phenyl vinyl silicone rubber, then intermittently processing for 50 minutes by using a high-speed emulsifying machine at the rotating speed of 30000rpm, then adding 5g of the component B of the two-component silicone rubber and continuously performing emulsification processing for 5 minutes at 10000rpm to uniformly mix the components, and vacuumizing and defoaming the obtained graphene/two-component silicone rubber dispersion liquid;
2. preparing graphene/methyl phenyl vinyl silicone rubber composite fiber by adopting a solution spinning method, wherein the inner diameter of a syringe needle is 0.5mm, the injection speed is 4cm/min, the temperature of methyl silicone oil is 180 ℃, and the heat treatment time of the fiber is 15min;
3. mixing the component A and the component B of the methyl phenyl vinyl silicone rubber, emulsifying for 5 minutes at 10000rpm, and vacuumizing to remove bubbles to obtain a methyl phenyl vinyl silicone rubber dispersion liquid;
4. preparing graphene/methyl phenyl vinyl silicone rubber coaxial fibers by adopting a coaxial solution spinning method, wherein the diameter of an inner tube of a coaxial needle is 1.0mm, the diameter of an outer tube of the coaxial needle is 1.5mm, the injection speed of core liquid is 10cm/min, and the injection speed of shell liquid is 8cm/min;
5. and mutually winding the graphene/methyl phenyl vinyl silicone rubber composite fiber and the graphene/methyl phenyl vinyl silicone rubber coaxial fiber to form an elastic twisted pair, and blending polyurethane fiber on the surface of the elastic twisted pair through a ring spinning machine to obtain the graphene/methyl phenyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn.
6. The graphene/methyl phenyl vinyl silicone rubber coaxial fiber-based elastic core-spun yarn is woven on wrist straps and gloves and used as a self-powered sensor to monitor human body movement.
The above embodiments are merely illustrative of the technical solutions of the present invention. The graphene/silicone rubber coaxial fiber-based elastic core-spun yarn, the preparation method and the application thereof are not limited to what is described in the above embodiments, but are subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.
Claims (8)
1. A preparation method of a graphene/silicone rubber coaxial fiber-based elastic core-spun yarn is characterized by comprising the following steps:
step 1, mixing expanded graphite with a component A (raw rubber) of the two-component silicon rubber, then processing for 10-60 minutes by using a high-speed emulsifying machine, stripping the expanded graphite under the adhesion and high-speed shearing action of the raw rubber to form few-layer or even single-layer graphene, then adding a component B (catalyst) of the two-component silicon rubber, continuing to perform emulsification processing for 2-10 minutes, and vacuumizing to remove bubbles to obtain a graphene/two-component silicon rubber dispersion liquid;
step 2, filling the graphene/two-component silicon rubber dispersion liquid obtained in the step 1 into an injector, and injecting the dispersion liquid into hot methyl silicone oil through injection equipment to thermally cure the two-component silicon rubber into fibers to obtain graphene/silicon rubber composite fibers;
step 3, mixing the component A and the component B of the double-component silicon rubber, carrying out high-speed shearing emulsification treatment for 2-10 minutes, and vacuumizing to remove bubbles to obtain a pure double-component silicon rubber dispersion liquid;
step 4, preparing the graphene/silicon rubber coaxial fiber by adopting a coaxial solution spinning method: respectively taking the graphene/double-component silicon rubber dispersion liquid obtained in the step 1 as a core layer and the pure double-component silicon rubber dispersion liquid obtained in the step 3 as a shell layer, subpackaging the two different injectors, respectively connecting the injectors to an inner tube and an outer tube of a coaxial needle, then injecting the two dispersion liquids into hot methyl silicone oil through injection equipment, and performing thermocuring to obtain graphene/silicon rubber coaxial fibers, wherein the core layer is graphene/silicon rubber composite fibers, and the shell layer is pure silicon rubber;
and 5, mutually winding the graphene/silicon rubber composite fiber obtained in the step 2 and the graphene/silicon rubber coaxial fiber obtained in the step 4 to form an elastic twisted wire or a multi-twisted wire, and blending chemical fiber on the surface of the elastic twisted wire or the multi-twisted wire to obtain the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn.
2. The preparation method of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn according to claim 1, characterized in that:
in the step 1, the bicomponent silicone rubber mainly comprises one of methyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber and fluorine silicone rubber, the mass ratio of the component A to the component B is 20 to 1, the mass ratio of the expanded graphite to the bicomponent silicone rubber is 1 to 100, and the shearing speed of the high-speed emulsifying machine is 5000 to 50000rpm.
3. The preparation method of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn according to claim 1, characterized in that:
in the step 2, the temperature of the hot methyl silicone oil is 100 to 200 ℃, the inner diameter of a syringe needle is 0.4 to 5mm, the injection speed is 1 to 20cm/min, and the heat treatment time of the composite fiber is 5 to 20min.
4. The preparation method of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn according to claim 1, characterized in that:
in the step 4, the diameter of an inner tube of the coaxial needle is 0.4 to 4mm, the diameter of an outer tube is 0.8 to 5mm, the diameter ratio of the inner tube to the outer tube is 1 to 4.
5. The preparation method of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn according to claim 1, characterized in that:
wherein, in the step 5, the blending is performed in a ring spinning machine or a rotor spinning machine, preferably a ring spinning machine.
6. The preparation method of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn according to claim 1, characterized in that:
wherein, in the step 5, the chemical fiber includes, but is not limited to, ethyl cellulose fiber, polyester fiber, polyamide fiber, polyurethane fiber, polyacrylonitrile fiber.
7. A graphene/silicone rubber coaxial fiber-based elastic core-spun yarn, which is prepared by the preparation method of any one of claims 1 to 6.
8. The use of the graphene/silicone rubber coaxial fiber-based elastic core-spun yarn according to claim 7, wherein:
the graphene/silicon rubber coaxial fiber-based elastic core-spun yarn is applied to the fields of friction nano-generators, flexible motion sensors and the like.
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