CN112022494A

CN112022494A - Palladium nanosheet/graphene-based traditional Chinese medicine hot compress device

Info

Publication number: CN112022494A
Application number: CN202010937484.8A
Authority: CN
Inventors: 吴立刚; 叶德林; 张以河; 马宇飞; 李明; 李正博
Original assignee: Beijing Kangene Technology Innovation Research Co ltd
Current assignee: Beijing Kangene Technology Innovation Research Co ltd
Priority date: 2020-09-08
Filing date: 2020-09-08
Publication date: 2020-12-04

Abstract

The invention provides a palladium nanosheet/graphene-based traditional Chinese medicine hot compress device which is characterized by comprising a hot compress sleeve and a palladium nanosheet/graphene-based heating film, wherein a first containing bag is arranged on the outer side of the hot compress sleeve and used for containing the palladium nanosheet/graphene-based heating film, a second containing bag is arranged on the inner side of the hot compress sleeve and used for containing a traditional Chinese medicine bag. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device disclosed by the invention realizes the electric heating and photo-thermal diversified heat production functions by means of the high-efficiency photo-thermal conversion efficiency and the electric heating conversion efficiency of the palladium nanosheet/graphene-based heating film, and has the effects of high active ingredient absorption rate, stable heat production and the like.

Description

Palladium nanosheet/graphene-based traditional Chinese medicine hot compress device

Technical Field

The invention relates to the technical field of graphene heating devices, in particular to a flexible palladium nanosheet/graphene-based traditional Chinese medicine hot compress device.

Background

Graphene is a hetero-substitution of carbon atoms through sp2The chemical orbitals form a hexagonal two-dimensional nano material which is in a honeycomb lattice structure and only has one layer of carbon atom thickness. The unique structure of graphene gives it a number of excellent properties, such as a high theoretical specific surface area (2630 m)²The material is prepared by the following raw materials, such as the raw materials of the material are selected from the following raw materials, such as/g), ultrahigh electron mobility (200000 cm2/v.s), high thermal conductivity (5300W/m.K), high Young modulus (1.0TPa), high light transmittance (97.7%) and the like. By virtue of the advantages of the structure and the performance of the graphene, the graphene has a huge application prospect in the fields of energy storage and conversion devices, nano-electronic devices, multifunctional sensors, flexible wearable electronics, electromagnetic shielding, corrosion prevention and the like. In view of the flexibility and the conductive characteristic of graphene, the graphene slurry is added into the printing ink to prepare the conductive printing ink, and the graphene heating layer is further prepared by spraying and drying the printing ink to prepare the graphene heating body.

Along with the trend of people to good and healthy life, the traditional heating system is improved, more economic and clean alternative energy is searched, and the development of a novel green low-carbon heating system is reluctant. An electric heating technology based on graphene infrared emission performance (far infrared rays with the wavelength of 5-14 microns), namely graphene-based infrared heating ink and an infrared heating body technology thereof, provides an effective solution for solving the problems. Compared with the traditional heating methods such as coal burning, steam, hot air and resistance, the graphene heating method has the advantages of high heating speed, high electricity-heat conversion rate, automatic temperature control, zone control, stable heating, no abnormal sound in the heating process, high heat conduction efficiency, low operation cost (the power consumption of each square meter of the graphene electrothermal film can be reduced to 0.5 degree every day), relatively uniform heating, small floor area, low investment and production cost, long service life, high working efficiency and the like, and is more favorable for popularization and application. The energy-saving heating device replaces the traditional heating device, has particularly remarkable electricity-saving effect, can generally save electricity by about 30 percent, and even can reach 60 to 70 percent in individual occasions.

In the prior art, graphene is generally prepared into graphene slurry, ink or paint, and then prepared into a graphene heating coating and the like through a printing method. For example, patent application No. CN 201911401440.7, the patent name of which is graphene far infrared heating brick, discloses a graphene far infrared heating brick, a brick unit of the floor heating brick comprises a heating element and a heat dissipation member, wherein the heating element is made of graphene composite coating, and the heat dissipation member is made of graphene composite rack. The graphene heating coating is printed on the base material, and the graphene heating coating prepared by printing is easily broken after being repeatedly folded and stretched, so that the graphene heating coating is broken, and the heat production effect and the service life of the graphene heating coating are influenced. In addition, the defects that the graphene heating coating has poor adhesion effect with a flexible substrate and is easy to separate after being used for a long time are still the subject of the industry.

Graphene fiber membrane is added into spinning solution, and further with the help of fiber membrane and fiber membrane-based heating device that electrostatic spinning technology prepared obtained, graphene fiber membrane has advantages such as flexible strong, resistant effectual, the surface area of buckling is big, and graphene fiber membrane need not adhere to the base plate, can form a film alone or bond on the flexible base plate through the adhesive after the film-forming for the heat supply. The traditional Chinese medicine hot compress is a common medicine application mode, can effectively promote the release of active ingredients of the traditional Chinese medicine, strengthen the absorption of organisms and improve the curative effect of the traditional Chinese medicine, and has important effects on treating and conditioning the gynecological symptoms such as female dysmenorrheal, cold uterus and the like. The current traditional Chinese medicine hot compress mode is as follows: wrapping the traditional Chinese medicine into a towel or other water absorption containing bag, soaking the whole towel or the water absorption containing bag in hot water, and applying the towel or the water absorption containing bag to the navel or other parts needing to be applied after the active ingredients of the traditional Chinese medicine are released to the towel or the water absorption containing bag. However, this application method can only ensure a short heating action, the release of the active pharmaceutical ingredient is limited, and it is difficult to transmit the active pharmaceutical ingredient to the epidermis for absorption by the body through the water vapor medium, and the therapeutic effect is greatly limited. Based on the high infrared normal emission amount, the high thermal efficiency, the high heat conduction efficiency and the thermal stability of the flexible graphene fiber membrane, the traditional Chinese medicine hot compress device is developed to solve the problems of slow absorption, small release amount of active ingredients, insignificant curative effect and the like in the current traditional Chinese medicine hot compress field, and becomes the core point of the technical scheme of the invention.

Disclosure of Invention

In view of the above, the invention provides a flexible palladium nanosheet/graphene-based traditional Chinese medicine hot compress device, which is used for solving the problems of slow absorption, small release amount of active ingredients, insignificant curative effect and the like of the existing hot compress equipment.

In a first aspect, the invention provides a palladium nanosheet/graphene-based traditional Chinese medicine hot compress device, which comprises a hot compress sleeve and a palladium nanosheet/graphene-based heating film, wherein a first containing bag is arranged on the outer side of the hot compress sleeve and used for containing the palladium nanosheet/graphene-based heating film, a second containing bag is arranged on the inner side of the hot compress sleeve and used for containing a traditional Chinese medicine bag;

the palladium nano sheet/graphene-based heating film comprises a first transparent insulating layer, an electrode, a second transparent insulating layer and a palladium nano sheet/graphene-based fiber film, wherein the first transparent insulating layer covers one surface of the palladium nano sheet/graphene-based fiber film, the second transparent insulating layer covers the other surface of the palladium nano sheet/graphene-based fiber film, one end of the electrode is electrically connected with the palladium nano sheet/graphene-based fiber film, the other end of the electrode extends out of the first transparent insulating layer or the second transparent insulating layer and is used for connecting a waterproof socket/plug, and correspondingly, the waterproof plug/socket is arranged in the first accommodating bag;

the preparation method of the palladium nanosheet/graphene-based fiber membrane comprises the following steps:

preparing a pre-stripping dispersion of palladium powder: providing palladium powder and adding the palladium powder into the pre-stripping dispersion liquid, performing primary water bath ultrasound on the pre-stripping dispersion liquid added with the palladium powder, wherein the temperature of the primary water bath ultrasound is 5-15 ℃, and centrifuging and collecting supernatant after the primary water bath ultrasound is finished to prepare the pre-stripping dispersion liquid of the palladium powder;

preparing a mixture of palladium powder and graphene oxide: adding graphene oxide into a pre-stripping dispersion liquid of palladium powder, performing secondary water bath ultrasound at the temperature of 5-15 ℃, centrifuging after the secondary water bath ultrasound is finished, collecting a bottom layer mixture, dispersing the bottom layer mixture in water, washing and drying to obtain a mixture of the palladium powder and the graphene oxide;

preparing a palladium nanosheet/graphene oxide dispersion liquid: dispersing a mixture of palladium powder and graphene oxide in DMF to prepare a mixed solution, performing ultrasonic treatment on the mixed solution by using a pulse probe at the ultrasonic temperature of 5-15 ℃, and concentrating the mixed solution after the ultrasonic treatment is finished to prepare a palladium nanosheet/graphene oxide dispersion solution;

spinning: adding carbon black and PAN powder into a palladium nanosheet/graphene oxide dispersion liquid, uniformly stirring, and then carrying out three-stage water bath ultrasound, wherein the temperature of the three-stage water bath ultrasound is 5-15 ℃, and after the three-stage water bath ultrasound is finished, the three-stage water bath ultrasound is used as a spinning stock solution, and electrostatic spinning and collection are carried out by using a spinning needle with the inner diameter increased along a filament outlet direction, so as to prepare the palladium nanosheet/graphene oxide hybrid porous fibrous membrane;

and (3) post-treatment: washing the palladium nanosheet/graphene oxide hybrid porous fiber membrane, drying and reducing to obtain a palladium nanosheet/graphene-based fiber membrane;

the mass of the graphene oxide is 0.5-5 times of the mass of the palladium powder in the pre-stripping dispersion liquid of the palladium powder, the mass fraction of PAN in the spinning stock solution is 8-12%, and the pre-stripping dispersion liquid is isopropanol, deionized water or a mixed solution of the isopropanol and the deionized water.

The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device comprises a hot compress sleeve and a palladium nanosheet/graphene-based heating film, wherein the palladium nanosheet/graphene-based heating film is detachably connected with the hot compress sleeve, so that the palladium nanosheet/graphene-based heating film is conveniently installed in the hot compress sleeve when in use, and the palladium nanosheet/graphene-based heating film is conveniently detached when not in use, so that the hot compress sleeve is conveniently cleaned. The photo-thermal and electro-thermal effects of the palladium nanosheet/graphene-based heating film are utilized to generate heat and emit a large amount of infrared rays, so that on one hand, the infrared rays promote blood circulation and pore opening, and the absorption effect is greatly improved; on the other hand, the infrared ray promotes the release of the active ingredients of the traditional Chinese medicine by heating the traditional Chinese medicine bag, greatly improves the release amount and the utilization rate of the active ingredients, and finally improves the comprehensive treatment and health care effects.

The palladium nanosheet/graphene-based heating film comprises a first transparent insulating layer, an electrode, a second transparent insulating layer and a palladium nanosheet/graphene-based fiber film, wherein the first transparent insulating layer and the second transparent insulating layer are attached to two sides of the palladium nanosheet/graphene-based fiber film, so that the palladium nanosheet/graphene-based fiber film is isolated in a closed insulating space, and electric leakage is prevented when the palladium nanosheet/graphene-based fiber film is electrified to generate heat. One end of the electrode is electrically connected with the palladium nanosheet/graphene-based fibrous membrane, and the other end of the electrode extends out of the first transparent insulating layer or the second transparent insulating layer, so that the palladium nanosheet/graphene-based fibrous membrane can be electrically conducted with an external power supply through the electrode. The first transparent insulating layer and the second transparent insulating layer can also ensure that the palladium nanosheet/graphene-based fiber membrane can receive light radiation, and by means of the high-efficiency photothermal conversion efficiency and the electric heating conversion efficiency of the palladium nanosheet/graphene-based fiber membrane, the diversified heat generation function integrating electric heating and photothermal is realized.

The preparation method of the palladium nanosheet/graphene-based fiber membrane comprises the steps of preparing a pre-stripping dispersion liquid of palladium powder, preparing a mixture of the palladium powder and graphene oxide, preparing the palladium nanosheet/graphene oxide dispersion liquid, spinning and post-treating. The step of preparing the pre-stripping dispersion liquid of the palladium powder can strip the palladium powder in advance, and the stripping efficiency of the palladium powder and the preparation efficiency of the palladium nanosheets are improved by collecting the preliminarily stripped palladium powder and using the palladium powder for the next stripping. In the step of preparing the mixture of the palladium powder and the graphene oxide, the preliminarily peeled palladium powder and the graphene oxide are subjected to water bath ultrasound together, the palladium powder has poor dispersibility in the pre-peeling dispersion liquid, the graphene is added into the pre-peeling dispersion liquid of the palladium powder and the water bath ultrasound is carried out together, and the palladium powder is effectively peeled and can be well mixed with the graphene oxide with the aid of the graphene. In the step of preparing the palladium nanosheet/graphene oxide dispersion liquid, the mixed liquid is subjected to ultrasonic treatment by adopting a pulse probe, so that the palladium nanosheet can be effectively prepared, and the palladium nanosheet and the graphene oxide dispersion liquid are further mixed, so that the phenomenon that the palladium nanosheet or the graphene oxide is stacked mutually to cause that the local concentration is too high and cannot be spun is prevented, and the conductivity and the dispersion uniformity among graphene sheet layers can be improved. The primary water bath ultrasound, the secondary water bath ultrasound and the pulse probe ultrasound are carried out at low temperature, so that the prepared palladium nanosheet can be effectively prevented from being degraded. In the spinning step, PAN powder and carbon black are added into a DMF solution, three-stage water bath ultrasound is performed after uniform stirring, the spinning solution is more uniform through the stirring and ultrasound processes, the uniformity of the physical size and the performance of the produced filament is ensured, the carbon black and the PAN powder can be fully dispersed in the palladium nanosheet/graphene oxide dispersion liquid, the uniform distribution and the uniform conductivity of the electric conductor of the spinning fiber are ensured, the electric conductor is fully doped on the PAN high molecular compound, and the palladium nanosheet/graphene oxide hybrid porous fiber with uniform conductivity is prepared. In the post-treatment step, the palladium nanosheet/graphene oxide hybrid porous fiber membrane is washed, dried and reduced, and the graphene oxide is reduced into reduced graphene oxide, so that the reduced palladium nanosheet/graphene-based fiber membrane is prepared, and has the advantages of stable chemical property, heat resistance, strong electric conductivity, high infrared radiance, integration of heat collecting property and photo-thermal property and the like.

According to the preparation method of the palladium nanosheet/graphene-based fiber membrane, the graphene oxide is added in the preparation process of the palladium nanosheet, so that the palladium powder can be assisted to be stripped into the palladium nanosheet, and the palladium nanosheet and the graphene oxide can be uniformly mixed. The palladium nanosheet, the graphene oxide and the carbon black are further loaded on the fiber in the spinning process, so that the fiber has the advantages of large specific surface area, strong infrared radiation, remarkable electrothermal and photothermal properties, high thermal conductivity, good flexibility, remarkable bending-resistant effect and the like, and the fiber also has the advantages of high mechanical strength, medium-high temperature resistance and the like due to the fact that a large amount of PAN (polyacrylonitrile) polymers are contained in the fiber.

Preferably, the outside of hot compress cover is equipped with the transparent lamella, the surface of transparent lamella and hot compress cover encloses into first holding bag. Through setting up the transparent lamella in order to ensure that illumination can penetrate the transparent lamella and enter into first holding bag, further on the light irradiation palladium nano sheet/graphite alkene base heating film, with the help of the light and heat conversion effect of palladium nano sheet/graphite alkene base heating film, can effectively produce heat with the help of illumination to further be used for the heat of production to pack in the hot compress. Especially, when the user is in outdoor activities or rest, for example walk or lie, the user only needs to carry out the traditional chinese medicine hot compress with palladium nanometer piece/graphite alkene base traditional chinese medicine hot compress device towards the one side in the outside and towards sunshine for this palladium nanometer piece/graphite alkene base traditional chinese medicine hot compress device does not receive the restriction of source position and produces heat, also has the effect of energy saving in addition.

More preferably, the transparent sheet layer is made of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), Polyimide (PI), Polycarbonate (PC), Polystyrene (PS) or ABS plastic.

Preferably, the inboard of hot compress cover is equipped with the barrier layer, be equipped with porous lamella in the one side of barrier layer dorsad hot compress cover, porous lamella encloses into the second with the barrier layer and holds the bag. Therefore, steam generated by heating can be effectively prevented from passing through the first containing bag and the palladium nano sheet/graphene-based heating film to be distributed out through the blocking layer arranged on the inner side of the hot compress sleeve, the first containing bag, the palladium nano sheet/graphene-based heating film and the like are prevented from being polluted, electric leakage and the like are avoided, and the steam generated by hot compress of traditional Chinese medicines can be promoted to be in contact with the epidermis of a pasting part and absorption is promoted. The porous sheet layer and the barrier layer enclose a second containing bag for containing the Chinese medicine bag, and steam generated by heating can diffuse out from the gaps of the porous sheet layer and contact with the epidermis.

More preferably, the material of the barrier layer may be Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), Polyimide (PI), Polycarbonate (PC), Polystyrene (PS), or ABS plastic, or may be a non-transparent plastic film. The porous sheet layer is cloth or other flexible netted sheet materials.

Preferably, a sealing ring is further arranged on one surface of the blocking layer, which faces away from the hot compress sleeve, and the sealing ring is arranged around the second accommodating bag;

the cross section of the sealing ring is arranged to be concave. Therefore, after the sealing ring is attached to the machine body, the sealing ring, the blocking layer and the surface skin jointly enclose a sealing cavity, the traditional Chinese medicine bag is contained in the sealing cavity, traditional Chinese medicine steam generated by heating is circulated in the sealing cavity, and the steam utilization rate and the medicine release rate are improved. Can effectively prevent the traditional chinese medicine steam that produces to diffusing at random all around through setting up the sealing washer that encircles the second and hold the bag, one can retrain the diffusion path of traditional chinese medicine steam, and the two also can promote the utilization ratio of traditional chinese medicine steam. The cross section of the sealing ring is arranged to be concave, and the concave sealing ring is attached to the surface to form a gas path sealing structure, so that the sealing ring has better sealing property.

More preferably, the material of sealing washer is silica gel, flexible resin or rubber, can be better with the epidermis laminating. The two ends of the cross section of the sealing ring are arched, the two ends of the arched sealing ring are tightly attached to the surface skin, and the sealing ring has a better airtight effect.

Preferably, the steam exhaust pipe penetrates through the sealing ring and is used for exhausting steam inside the sealing ring;

the pressure limiting valve is arranged on the steam discharge pipe and used for controlling the air pressure in the sealing ring. Therefore, the steam can be drained to a specific direction and position through the arranged steam drainage pipe, and the phenomenon that the steam overflows to pollute the device or cause waste of the steam is prevented. The pressure of a sealed cavity formed by the sealing ring, the blocking layer and the epidermis can be adjusted by arranging the pressure limiting valve, so that the absorption rate of the active ingredients of the traditional Chinese medicine is improved.

Preferably, one end of the hot compress sleeve is provided with a male buckle, and the other end of the hot compress sleeve is provided with a female buckle;

the traditional Chinese medicine bag is made of sponge materials, and an opening capable of being opened and closed is formed in one side of the traditional Chinese medicine bag. The hot compress sleeve is fixed by the male buckle and the female buckle. The traditional Chinese medicine bag is made of sponge materials, can effectively promote the active ingredients of the traditional Chinese medicine to diffuse out by means of a steam carrier, and further acts on epidermis. When the traditional Chinese medicine bag is placed, the water can absorb water, and steam can be further generated by means of the absorbed water in the subsequent hot compress process, so that the release of the active ingredients of the traditional Chinese medicine is promoted. One side of the traditional Chinese medicine bag is provided with an opening which can be opened and closed, so that different traditional Chinese medicinal materials such as common achyranthes, moxa, pepper, anise, cassia bark, clove, asarum, mint, fennel, ginger, sea salt, angelica, motherwort, amber and the like can be conveniently replaced, some spices such as petals of rose, clove, lily, lavender and the like can also be placed, and hot compress can be directly carried out after purified traditional Chinese medicine active ingredients are sprayed in the traditional Chinese medicine bag.

Preferably, a transparent heat conduction layer is further arranged between the second transparent insulation layer and the palladium nanosheet/graphene-based fiber membrane. By arranging the transparent heat conduction layer, on one hand, light radiation cannot be influenced to penetrate through the transparent heat conduction layer and act on the palladium nanosheet/graphene-based fiber membrane, and photo-thermal conversion is realized; on the other hand, the transparent heat conducting layer can also efficiently conduct out heat and infrared radiation generated after the palladium nanosheet/graphene-based fiber membrane is electrified.

Preferably, a waterproof bonding layer is further arranged between the first transparent insulating layer and the second transparent insulating layer, and the waterproof bonding layer is bonded with the first transparent insulating layer and the second transparent insulating layer respectively to form a closed cavity;

the palladium nanosheet/graphene-based fiber membrane and the transparent heat conduction layer are both arranged in the closed cavity, and the electrode extends out of the closed cavity. The first transparent insulating layer and the second transparent insulating layer are respectively bonded with the waterproof bonding layer to form a closed cavity, and the palladium nanosheet/graphene-based fiber membrane and the transparent heat conducting layer are arranged in the closed cavity, so that a good insulating and waterproof effect is achieved.

Preferably, the electrode comprises a transverse arm and a vertical arm which are connected with each other, the transverse arm extends out of the transparent heat conduction layer to form the closed cavity, and the vertical arm extends out of the transparent heat conduction layer and is electrically connected with the palladium nanosheet/graphene-based fiber membrane. The electrodes are arranged in an L shape and comprise a transverse arm and a vertical arm which are mutually connected, the electric connection between the palladium nanosheet/graphene-based fiber membrane and an external power supply can be realized by means of the L-shaped electrodes, the fact that the palladium nanosheet/graphene-based fiber membrane receives illumination from the first transparent insulating layer is not influenced, and a closed waterproof cavity can be formed in an L-shaped loop, so that the waterproof effect of the palladium nanosheet/graphene-based heating membrane is facilitated.

Preferably, the heat reflection type solar cell further comprises a heat reflection layer which is arranged in a concave shape to form an accommodating groove;

the first transparent insulating layer and the palladium nanosheet/graphene-based fiber membrane are arranged in the accommodating groove. The first transparent insulating layer and the palladium nanosheet/graphene-based fiber membrane are arranged in the accommodating groove to form a waterproof loop structure, so that electric leakage of the palladium nanosheet/graphene-based fiber membrane is prevented. In addition, one bottom surface and the peripheral side wall of the palladium nanosheet/graphene-based fiber membrane are covered by the concave heat reflecting layer, so that the palladium nanosheet/graphene-based fiber membrane can only radiate heat from the opening direction of the heat reflecting layer when being electrified to generate heat, and the heat reflecting layer has the effects of restraining the infrared radiation direction, controlling the heat conduction direction and improving the heat utilization rate.

Preferably, one end of the transparent heat conduction layer, which faces the palladium nanosheet/graphene-based fiber membrane, is embedded into the accommodating groove, and one end of the transparent heat conduction layer, which faces the second transparent insulation layer, is connected with the second transparent insulation layer. The transparent heat conduction layer is embedded into the accommodating groove towards one end of the palladium nanosheet/graphene-based fiber membrane to form a waterproof loop structure, so that electric leakage of the palladium nanosheet/graphene-based fiber membrane is prevented.

Preferably, the heat reflecting layer includes a reflecting film and an insulating film, the reflecting film covering an outer surface of the insulating film;

the insulating film is equipped with the flange towards the one end of second transparent insulation layer, be equipped with the draw-in groove that is used for the holding flange on the periphery wall of waterproof adhesive linkage. Can effectively prevent palladium nanometer piece/graphite alkene base fiber membrane and reflectance coating direct contact and electric leakage through setting up reflectance coating and insulating film, set up to dismantling the connected mode between insulating film and the waterproof adhesive layer. The heat reflective layer can be removed when light conduction from the first transparent insulating layer is required, thereby realizing continuous photothermal conversion. When needing circular telegram to produce heat, circular telegram with palladium nano sheet/graphite alkene base fiber membrane closes the heat reflection stratum, can prevent effectively from the diffusion of heat from first transparent insulation layer from this, has restraint infrared radiation direction, control heat-conduction direction, improves heat utilization rate's effect.

Preferably, the reflective film is an aluminum foil film or a silver foil film, and the insulating film is a flexible resin film. By virtue of the flexibility of the flexible resin film and the toughness of the aluminum foil or silver foil, the covering of the heat reflecting layer can be easily achieved by deformation.

Preferably, in the step of preparing the pre-stripping dispersion liquid of the palladium powder, the mass-volume ratio of the palladium powder to the pre-stripping dispersion liquid is 10-500 mg/ml, the power of the primary water bath ultrasound is 250-500W, and the time of the primary water bath ultrasound is 24-72 h;

the rotating speed of the centrifugation is 1500-3500 RPM, and the time of the centrifugation is 5-30 min. The function of pre-stripping the palladium simple substance can be achieved through primary water bath ultrasound, the subsequent centrifugal process can separate the pre-stripped few-layer palladium simple substance from un-stripped palladium powder, the small palladium simple substance generated by pre-stripping is transferred to the next stripping procedure, and the few-layer palladium nanosheet is efficiently prepared.

Preferably, in the step of preparing the mixture of palladium powder and graphene oxide, the power of the secondary water bath ultrasound is 250-500W, and the time of the secondary water bath ultrasound is 8-24 h;

the rotating speed of the centrifugation is 8000-15000 RPM, and the time of the centrifugation is 20-100 min. After adding the graphene oxide, mixing the graphene oxide with the preliminarily peeled palladium powder, further performing secondary water bath ultrasound, mixing the graphene oxide with the preliminarily peeled palladium powder, wherein the graphene oxide has the effect of assisting the peeling and dispersion of the palladium powder, and preventing the palladium nanosheets and the graphene oxide from being stacked mutually. And further collecting the palladium nanosheets and graphene oxide generated by stripping through centrifugation for subsequent steps.

Preferably, in the step of preparing the mixture of palladium powder and graphene oxide, the mixture of the bottom layer is dispersed in water for washing, then the solvent is concentrated and removed by using a rotary evaporation method, and the concentrated mixture is transferred to a temperature of 30-40 ℃ for vacuum drying for 2-8 hours to prepare the mixture of the palladium powder and the graphene oxide. The method has the advantages that the residual pre-stripping dispersion liquid on the mixture of the palladium powder and the graphene oxide can be effectively removed through the steps of removing the solvent by rotary evaporation, drying in vacuum and the like, the subsequent steps of preparing the palladium nanosheet/graphene oxide dispersion liquid and spinning are facilitated, the spinnability of the spinning solution is improved, and meanwhile, the concentration of the palladium nanosheet/graphene oxide dispersion liquid is conveniently measured.

Preferably, in the step of preparing the palladium nanosheet/graphene oxide dispersion liquid, the mass-to-volume ratio of the mixture of the palladium powder and the graphene oxide to the DMF is 1-10 mg/ml, the ultrasonic time of the pulse probe is 2-12 h, the ultrasonic power of the pulse probe is 200-300W, and the ultrasonic frequency of the pulse probe is set as: ultrasound 5s, interval 5 s. Therefore, the mixture of palladium powder and graphene oxide can be promoted to be well dispersed in DMF through pulse probe ultrasound, so that a dispersion liquid with good dispersion of palladium nanosheets and graphene oxide is prepared, and preparation is made for preparing a spinning solution subsequently.

Preferably, in the step of preparing the palladium nanosheet/graphene oxide dispersion liquid, after the ultrasonic treatment is finished, the mixed liquid is concentrated by a vacuum rotary evaporation method until the solid content is 10-50 mg/ml;

the vacuum degree of the vacuum rotary evaporation method is 0.05-0.08 MPa, and the temperature of the vacuum rotary evaporation method is 55-65 ℃. The palladium nanosheet/graphene oxide dispersion liquid is prepared through two steps, namely the palladium nanosheet and the graphene oxide are firstly dispersed at low concentration and then concentrated to reach the high concentration required by spinning, so that the palladium nanosheet and the graphene oxide can be well dispersed in DMF, the conductive requirement of a fiber membrane can be met, the content of a conductive body in the palladium nanosheet/graphene-based fiber membrane can be effectively increased by concentrating the mixed liquid through a vacuum rotary evaporation method, and the conductivity of the fiber membrane is increased.

Preferably, in the spinning step, the mass-to-volume ratio of the carbon black to the palladium nanosheet/graphene oxide dispersion is 50-100 mg/ml;

the time of the three-stage water bath ultrasound is 4-12 hours, the power of the three-stage water bath ultrasound is 250-500W, and the collection is realized by collecting palladium nanosheets/graphene oxide hybrid porous fibers by adopting a collecting plate. The addition of the carbon black can further improve the conductivity of the palladium nanosheet/graphene-based fiber membrane, regulate and control the ratio of the carbon black to the palladium nanosheet/graphene oxide dispersion liquid, improve the conductivity of the palladium nanosheet/graphene-based fiber membrane, avoid the influence of excessive use of the carbon black on the spinnability of a spinning solution, and reduce the flexibility of the palladium nanosheet/graphene-based fiber membrane. The palladium nanosheet, the graphene oxide and the carbon black are further stripped and dispersed through three-stage water bath ultrasound to prepare a conductive body with a smaller size, so that the conductive body can be uniformly doped into the palladium nanosheet/graphene hybrid porous fiber, and the palladium nanosheet/graphene-based fiber membrane with good flexibility, high conductivity, excellent heat resistance and strong mechanical property is prepared.

Preferably, in the spinning step, the inner diameter of the thin end of the spinning needle head is 0.3mm, the inner diameter of the thick end of the spinning needle head is 0.36mm, the electrostatic spinning voltage is 20-50 KV, and the receiving distance is 10-30 cm. Therefore, through carrying out electrostatic spinning by using the spinning needle with the inner diameter increased along the filament outlet direction, the fluid velocity of the spinning stock solution forms sudden drop and generates outward component velocity along the radial direction, so that the palladium nanosheets and the graphene oxide are distributed along the radial direction, and the palladium nanosheets/graphene oxide hybrid porous fibers formed after curing have a large number of pore-shaped structures distributed along the radial direction, so that the palladium nanosheets/graphene oxide hybrid porous fibers have good radial flexibility and axial elasticity, and the palladium nanosheets/graphene oxide hybrid porous fiber membranes also have good flexibility and elasticity in all directions.

Preferably, in the post-treatment step, the palladium nanosheet/graphene oxide hybrid porous fiber membrane is washed by deionized water for 1-3 times, and the palladium nanosheet/graphene oxide hybrid porous fiber membrane is transferred to a vacuum drying oven at the temperature of 60-85 ℃ for drying for 4-12 hours;

soaking the dried palladium nanosheet/graphene oxide hybrid porous fiber membrane in HI and NaBH₄And hydrazine hydrate and ascorbic acid, and preparing the palladium nanosheet/graphene-based fiber membrane. The residual DMF in the palladium nanosheet/graphene-based fiber membrane is removed through the washing and drying processes, so that the PAN/palladium nanosheet/graphene oxide hybrid porous fiber membrane is prepared, and the washed and dried PAN/palladium nanosheet/graphene oxide hybrid porous fiber membrane has higher porosity and larger specific surface area and flexibility. And finally, the graphene oxide is reduced into reduced graphene oxide through a reduction process, and the reduced palladium nanosheet/graphene-based fiber membrane has better environmental stability and heat resistance, so that the service life of the palladium nanosheet/graphene-based fiber membrane is effectively prolonged.

The palladium nanosheet/graphene-based fiber membrane has the advantages of high porosity, good flexibility, large specific surface area, high conductivity, high electrothermal conversion efficiency, high photo-thermal conversion rate, high infrared emissivity, high heat conduction efficiency and the like, and also has obvious sterilization and bacteriostasis effects. When the palladium nanosheet/graphene-based fiber membrane is applied to floor heating, physical therapy or clothes, the palladium nanosheet/graphene-based fiber membrane also has the effect of infrared physical therapy. The basic fiber material of the palladium nanosheet/graphene-based fiber membrane is Polyacrylonitrile (PAN), so that the palladium nanosheet/graphene-based fiber membrane has the advantages of high mechanical property, medium-high temperature resistance, difficulty in aging and the like. When the palladium nanosheet/graphene-based fiber film is applied to a heating device, the palladium nanosheet/graphene-based fiber film has the advantages of uniform heat generation, stable heating performance, high infrared emission performance, medium-high temperature resistance and the like, and is low in attenuation rate after long-time use.

Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.

Drawings

In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a schematic front view of a palladium nanosheet/graphene-based traditional Chinese medicine hot compress device according to one embodiment of the present invention;

FIG. 2 is a schematic view of a backside structure of the palladium nanosheet/graphene-based traditional Chinese medicine hot compress device shown in FIG. 1;

FIG. 3 is a schematic structural view of the palladium nanosheet/graphene-based traditional Chinese medicine hot compress device shown in FIG. 1 in a use state;

FIG. 4 is a schematic cross-sectional view of a sealing ring of the palladium nanosheet/graphene-based traditional Chinese medicine hot compress device shown in FIG. 2;

FIG. 5 is a schematic view of a structure of a Chinese medicinal bag;

FIG. 6 is a schematic structural diagram of a palladium nanosheet/graphene-based heating film according to an embodiment of the present invention;

fig. 7 is a graph showing the test of photothermal conversion performance (240s, which corresponds to example 4, comparative example 2, comparative example 3, and comparative example 1 in this order from top to bottom).

Detailed Description

While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

As shown in fig. 1 to 6, a palladium nanosheet/graphene-based traditional Chinese medicine hot compress device according to an embodiment of the present invention is provided. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device comprises a hot compress sleeve 1 and a palladium nanosheet/graphene-based heating film 2. Wherein, the outside of hot compress cover 1 is equipped with first holding bag 11, and first holding bag 11 is used for holding palladium nanometer piece/graphite alkene base heating film 2. The inner side of the hot compress sleeve 1 is provided with a second containing bag 12, and the second containing bag 12 is used for containing the traditional Chinese medicine bag 3. A waterproof plug/socket 13 is further arranged in the first accommodating bag 11, and the waterproof plug/socket 13 is used for being electrically connected with the palladium nanosheet/graphene-based heating film 2 so as to supply power to the palladium nanosheet/graphene-based heating film 2.

Furthermore, the outer side of the hot compress sleeve 1 is provided with a transparent sheet layer, and the transparent sheet layer and the outer surface of the hot compress sleeve 1 are encircled to form a first containing bag 11. In a specific embodiment, the transparent sheet layer is connected with three sides of the outer surface of the heat pack 1, and only one opening is reserved for placing or taking out the palladium nanosheet/graphene-based heating film 2.

Furthermore, the outside of the hot compress sleeve 1 can be provided with a temperature control switch and a temperature display screen for controlling the heat production power and temperature of the palladium nanosheet/graphene-based traditional Chinese medicine hot compress device.

Further, the inboard of hot compress cover 1 is equipped with barrier layer 14, and barrier layer 14 laminates in the inboard of hot compress cover 1, and barrier layer 14 is equipped with porous lamella in the one side of hot compress cover 1 dorsad, and porous lamella encloses into the second with the barrier layer and holds bag 12. In a particular embodiment, the porous sheet is attached to the barrier layer on three sides, leaving only one opening for receiving or removing the medicated bag 3.

Further, the transparent sheet layer can be provided with a connecting piece for connecting the outer surface of the hot compress sleeve 1, so that the opening of the first containing bag 11 is closed or opened, and the effect of fixing the palladium nanosheet/graphene-based heating film 2 is achieved. Furthermore, the transparent sheet layer is made of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), Polyimide (PI), Polycarbonate (PC), Polystyrene (PS) or ABS plastic, so that electric leakage can be effectively prevented while light transmission is guaranteed.

Furthermore, a connecting member can be disposed on the porous sheet layer for connecting the barrier layer 14, so as to close or open the opening of the second containing bag 12, and to fix the traditional Chinese medicine bag 3.

Further, the material of the barrier layer 14 may be Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), Polyimide (PI), Polycarbonate (PC), Polystyrene (PS), or ABS plastic, or may be a non-transparent plastic film. The barrier layer 14 can prevent the vapor from passing through the first containing bag and the palladium nano-sheet/graphene-based heating film to be emitted, and can also prevent the electric leakage.

Furthermore, a sealing ring 15 is arranged on one surface of the barrier layer 14, which faces away from the hot compress sleeve 1, and the sealing ring 15 is arranged around the second containing bag 12. Therefore, after the sealing ring 15 is attached to the machine body, the sealing ring 15, the barrier layer 14 and the surface skin jointly enclose a sealing cavity, one end of the sealing ring 15 is abutted to the barrier layer 14, and the other end of the sealing ring 15 is abutted to the surface skin, so that the effect of sealing steam is achieved.

Further, the cross section of the sealing ring 15 is arranged to be concave, and the two sides of the concave sealing ring 15 are abutted to the surface skin to form a good sealing structure. Furthermore, the concave sealing ring 15 is arched on both sides, and the arched contact surface has better sealing effect. Furthermore, the material of the sealing ring 15 is silica gel, flexible resin or rubber.

Further, the steam exhaust pipe 16 and the pressure limiting valve 17 are included, and the steam exhaust pipe 16 penetrates through the sealing ring 15 and is used for exhausting steam inside the sealing ring 15. The pressure limiting valve 17 is arranged on the steam discharge pipe 16 and used for controlling the air pressure in the sealing ring 15. For example, when the air pressure in the sealed cavity enclosed by the sealing ring, the barrier layer and the skin reaches a certain threshold value, the pressure limiting valve 17 opens to release the pressure, thereby playing a role in controlling the vapor pressure.

Furthermore, one end of the hot compress sleeve 1 is provided with a male buckle, and the other end of the hot compress sleeve 1 is provided with a female buckle. The male and female fasteners are connected to fix the thermal compress pack 1 to the body, which may be around the waist, for example.

Further, the palladium nanosheet/graphene-based traditional Chinese medicine hot compress device further comprises a traditional Chinese medicine bag 3, wherein the traditional Chinese medicine bag 3 is made of sponge materials, and in other embodiments, the traditional Chinese medicine bag 3 can also be made of materials with porous structures, such as cloth materials. The top end of the traditional Chinese medicine bag 3 is also provided with an opening which can be opened and closed, the traditional Chinese medicine in the traditional Chinese medicine bag 3 can be replaced by opening the opening, and the opening is bonded through a thread gluing or a magnetic strip, so that the opening and the closing are convenient.

In the embodiment of the present invention, as shown in fig. 6, the palladium nanosheet/graphene-based heating film 2 includes a first transparent insulating layer 21, an electrode 22, a second transparent insulating layer 23, and a palladium nanosheet/graphene-based fibrous film 24. The first transparent insulating layer 21 covers the upper surface of the palladium nanosheet/graphene-based fiber membrane 24, and the second transparent insulating layer 23 covers the lower surface of the palladium nanosheet/graphene-based fiber membrane 24, so that the palladium nanosheet/graphene-based fiber membrane 24 is isolated in a closed insulating space, and electric leakage is prevented when the palladium nanosheet/graphene-based fiber membrane 24 generates heat when electricity is conducted. One end of the electrode 22 is electrically connected to the palladium nanosheet/graphene-based fiber membrane 24, and specifically, the electrode 22 may penetrate through the palladium nanosheet/graphene-based fiber membrane 24 or press the electrode 22 through the palladium nanosheet/graphene-based fiber membrane 24. The other end of the electrode 22 extends out of the first transparent insulating layer 21 (or extends out of the second transparent insulating layer 23, and also has the function of electrically connecting the palladium nanosheet/graphene-based fiber membrane 24 and the function of waterproofing), that is, the electrode 22 extends to the outside from the inside of the insulating space between the first transparent insulating layer 21 and the second transparent insulating layer 23, so that the palladium nanosheet/graphene-based fiber membrane 24 is electrically conducted with an external power supply. The first transparent insulating layer 21 and the second transparent insulating layer 23 can also ensure that the palladium nanosheet/graphene-based fiber membrane 24 can receive light radiation, and the electric heating and light-heat diversified heat generation functions are realized by means of the high-efficiency light-heat conversion efficiency of the palladium nanosheet/graphene-based fiber membrane 24.

Further, the material of the first transparent insulating layer 21 and the second transparent insulating layer 23 may be PET or PI.

Further, a transparent heat conduction layer 25 is further arranged between the second transparent insulation layer 23 and the palladium nanosheet/graphene-based fiber membrane 24. The transparent heat conducting layer 25 may be a transparent heat conducting glue or a flexible water bag (for example, water contained in a transparent film), which allows light to pass through without affecting the photothermal conversion of the palladium nanosheet/graphene-based fiber membrane 24; the transparent heat conducting layers 25 of the two layers have larger specific heat capacity generally and can play a certain heat storage role.

Further, a waterproof adhesive layer 26 is further disposed between the first transparent insulating layer 21 and the second transparent insulating layer 23, and the waterproof adhesive layer 26 is respectively adhered to the first transparent insulating layer 21 and the second transparent insulating layer 23 to form a closed cavity. The palladium nanosheet/graphene-based fiber membrane 24 and the transparent heat conduction layer 25 are both arranged in the closed cavity, and the electrode 22 extends from the inside of the closed cavity to the outside of the closed cavity.

Further, the electrode 22 includes a transverse arm and a vertical arm which are connected perpendicularly to each other, the transverse arm extends out of the transparent heat conduction layer 25 transversely to form a closed cavity, and the vertical arm extends out of the transparent heat conduction layer 25 longitudinally and is electrically connected with the palladium nanosheet/graphene-based fiber membrane 24. In other embodiments, the electrode 22 may have other structures, and only the palladium nanosheet/graphene-based fiber membrane 24 is ensured to be electrically conducted to the outside through the electrode 22.

Further, a heat reflecting layer 27 is further included, and the heat reflecting layer 27 is provided in a concave shape to form the receiving recess 273. The first transparent insulating layer 21 and the palladium nanosheet/graphene-based fiber membrane 24 are disposed in the accommodating recess 273. The heat reflection layer 27 may be fixedly connected or detachably connected to the first transparent insulation layer 21, the waterproof adhesive layer 26 or the second transparent insulation layer 23.

Further, the heat reflecting layer 27 includes a reflecting film 271 and an insulating film 272, and the reflecting film 271 covers the outer surface of the insulating film 272.

Further, a flange 274 is provided at an end of the insulating film 272 facing the second transparent insulating layer 23, and a locking groove 261 for receiving the flange 274 is provided on an outer peripheral wall of the waterproof adhesive layer 26. The heat reflecting layer 27 and the waterproof adhesive layer 26 are detachably connected by the flange 274 and the card slot 261.

Further, the reflective film 271 is an aluminum foil film or a silver foil film, and the insulating film 272 is a flexible resin film. In other embodiments, the heat reflective layer 27 may also be coated glass.

In the present embodiment, the following describes in detail the preparation method of the palladium nanosheet/graphene-based fibrous membrane and the prepared palladium nanosheet/graphene-based fibrous membrane by means of specific examples, including examples and comparative examples (hereinafter referred to as "comparative examples"), which are set with reference to the parameter ranges of example 4 for discussing the effects of the respective parameters on the performance of the palladium nanosheet/graphene-based fibrous membrane.

A preparation method of a palladium nanosheet/graphene-based fiber membrane comprises the following steps:

preparing a pre-stripping dispersion of palladium powder: palladium powder was provided and added to the pre-peeling dispersion, the type of pre-peeling dispersion (the pre-peeling dispersion in examples 7 and 8 was a mixed pre-peeling dispersion with a mass ratio of deionized water to isopropyl alcohol of 1: 1) and the concentration of palladium powder in the pre-peeling dispersion are shown in table 1. The pre-stripped dispersion added with palladium powder is subjected to primary water bath ultrasound, wherein the temperature (the primary water bath ultrasound is referred to as "one-pass" for short, the temperature here is a temperature value set by a water bath kettle, and the actual water bath temperature has a certain fluctuation), power and ultrasound time of the primary water bath ultrasound are shown in table 1. And after the ultrasonic treatment is finished, centrifuging the pre-stripping dispersion liquid added with the palladium powder, and collecting supernatant to prepare the pre-stripping dispersion liquid of the palladium powder, wherein the centrifugal rotating speed and the centrifugal time are shown in table 1.

TABLE 1 parameters of Pre-strip Dispersion procedure for preparation of Palladium powder

Preparing a mixture of palladium powder and graphene oxide: to the previously prepared pre-exfoliated dispersion of palladium powder, graphene oxide was added, where the ratio of the mass of graphene oxide to the mass of palladium powder in the supernatant (where palladium powder in the supernatant refers to the palladium powder dispersed in the supernatant, and the mass of palladium powder in the supernatant can be obtained by subtracting the mass of palladium powder centrifugally precipitated in the pre-exfoliation step from the mass of total palladium powder provided) is seen in table 2. After the addition of graphene oxide, the pre-exfoliated dispersion liquid of graphene oxide and palladium powder was transferred to a water bath kettle for secondary water bath ultrasound, wherein the temperature (referred to as "secondary ultrasound" for short) of the secondary water bath ultrasound, the power and the ultrasound time are shown in table 2. And after the secondary water bath ultrasound treatment is finished, centrifuging the pre-stripping dispersion liquid of the palladium powder added with the graphene oxide, and collecting a bottom layer mixture, wherein the centrifugal rotating speed and the centrifugal time are shown in table 2. And dispersing the bottom layer mixture in water, oscillating and washing the bottom layer mixture, transferring the washed mixture into a vacuum rotary evaporator for rotary evaporation to remove the pre-stripping dispersion liquid, transferring the rotary-evaporated mixture into a vacuum drying oven for drying, wherein the temperature and the drying time of the drying oven are shown in table 2.

TABLE 2 parameters of the procedure for preparing the mixture of palladium powder and graphene oxide

Preparing a palladium nanosheet/graphene oxide dispersion liquid: the mixture of palladium powder and graphene oxide was dispersed in DMF (N, N-dimethylformamide) to prepare a mixed solution, wherein the concentration of the mixture of palladium powder and graphene oxide (referred to as "mixture concentration") is shown in table 3. Performing ultrasound on a DMF solution of a mixture of palladium powder and graphene oxide by using a pulse probe, wherein the frequency of the pulse probe ultrasound is set as follows: ultrasound 5s, interval 5s, wherein the temperature of the pulse probe ultrasound (abbreviated as "pulse ultrasound"), the power of the pulse probe ultrasound, and the time of the pulse probe ultrasound are shown in table 3. After the pulse probe finishes the ultrasonic treatment, the mixed solution is concentrated by a vacuum rotary evaporation method, and the specific temperature and the vacuum degree of the vacuum rotary evaporation method (referred to as rotary evaporation for short) are shown in table 3. The concentration of the solid content of the concentrated mixture (here, the solid content can be measured by high-speed centrifugation, drying, etc.) is shown in table 3. And concentrating to obtain the palladium nanosheet/graphene oxide dispersion liquid.

TABLE 3 parameters of the procedure for preparing the palladium nanosheet/graphene oxide dispersion

Spinning: carbon black and PAN powder are added to the prepared palladium nanosheet/graphene oxide dispersion, specifically, the mass-to-volume ratio of the carbon black to the palladium nanosheet/graphene oxide dispersion (the ratio of the mass of the carbon black to the volume of the palladium nanosheet/graphene oxide dispersion, referred to as "carbon black concentration"), and the mass fraction of PAN after PAN powder addition (mass fraction of PAN in the whole system) are shown in table 4. Stirring the palladium nanosheet/graphene oxide dispersion liquid until the carbon black and the PAN powder are uniformly dispersed, and then performing three-stage water bath ultrasound (referred to as "three-stage ultrasound"), wherein specific stirring speed, stirring time, temperature of the three-stage water bath ultrasound, power of the three-stage water bath ultrasound and time of the three-stage water bath ultrasound are shown in table 4. After the ultrasound is finished, the spinning solution is directly used for electrostatic spinning, a spinning needle with the inner diameter increased along the yarn outlet direction is used, the inner diameter of the thin end of the spinning needle is 0.3mm, the inner diameter of the thick end of the spinning needle is 0.36mm, the receiving distance is 20cm, and the voltage of the specific electrostatic spinning is shown in table 4.

TABLE 4 parameters of the spinning step

And (3) post-treatment: and (3) washing the palladium nanosheet/graphene oxide hybrid porous fiber membrane by using deionized water, drying in vacuum, and repeating the washing and drying processes once. Soaking the washed palladium nanosheet/graphene oxide hybrid porous fiber membrane in a reducing agent for reduction, wherein the specific type of the reducing agent can be HI or NaBH₄Any of hydrazine hydrate and ascorbic acid, the kind of reducing agent in specific examples, reduction time are shown in table 5. And repeating the washing and drying processes for 1-2 times after reduction to obtain the palladium nanosheet/graphene-based fiber membrane.

TABLE 5 parameters of the post-treatment step

Comparative example 1

Comparative example 1 the setup was made with reference to example 4, comparative example 1 differing from example 4 only in that: the steps of preparing the palladium nanosheet, and carrying out secondary water bath ultrasound, pulse probe ultrasound, spinning and post-treatment on the palladium nanosheet and the graphene oxide together are omitted.

A preparation method of a graphene-based fiber membrane comprises the following steps:

preparing a mixture of graphene oxide: adding graphene oxide to the isopropanol pre-stripping dispersion liquid, wherein the ratio of the mass of the graphene oxide to the volume of the isopropanol is 100 mg/ml. After the addition of graphene oxide, the pre-exfoliated dispersion of graphene oxide was transferred to a water bath kettle for secondary water bath ultrasound, wherein the temperature (secondary water bath ultrasound is simply referred to as "secondary ultrasound", and the temperature here is also a temperature value set for the water bath kettle), power, and ultrasound time of the secondary water bath ultrasound were the same as those of example 4. And after the secondary water bath ultrasound is finished, centrifuging the pre-stripping dispersion liquid added with the graphene oxide, and collecting a bottom layer mixture, wherein the centrifugal speed and the centrifugal time are the same as those in the embodiment 4. And dispersing the bottom layer mixture in water, oscillating and washing the bottom layer mixture, transferring the washed mixture into a vacuum rotary evaporator for rotary evaporation to remove the pre-stripping dispersion, transferring the rotary evaporated mixture into a vacuum drying oven for drying, wherein the temperature and the drying time of the drying oven are the same as those of the example 4.

Preparing a graphene oxide dispersion liquid: similarly to example 4, the mixture of graphene oxide prepared above was dispersed in DMF to prepare a mixed solution, and then subjected to pulse probe ultrasound and concentration in this order to prepare a graphene oxide dispersion.

Spinning: in the same manner as in example 4, carbon black and PAN powder were added to the graphene oxide dispersion liquid prepared above, specifically, the mass-to-volume ratio of carbon black to graphene oxide dispersion liquid was 80mg/ml, and the mass fraction of PAN was 9%, and the processes of stirring, three-stage water bath ultrasound, spinning, and the like were sequentially performed to prepare a graphene-based fiber membrane.

And (3) post-treatment: refer to example 4.

Comparative example 2

preparing a pre-stripping dispersion of palladium powder: refer to example 4.

Preparing a mixture of palladium powder and graphene oxide: to the previously prepared pre-exfoliated dispersion of palladium powder, graphene oxide was added, wherein the ratio of the mass of graphene oxide to the mass of palladium powder in the supernatant was with reference to example 4. The pre-exfoliated dispersion of palladium powder with added graphene oxide was centrifuged, and the bottom layer mixture was collected, where the centrifugation speed, the centrifugation time, and the like were as in example 4. The bottom layer mixture was dispersed in water, the bottom layer mixture was washed by shaking, the washed mixture was transferred to a vacuum rotary evaporator to remove the pre-peeling dispersion by rotary evaporation, and the rotary evaporated mixture was transferred to a vacuum drying oven to be dried, the temperature and drying time of the oven were as in example 4.

Preparing a palladium nanosheet/graphene oxide dispersion liquid: refer to example 4.

Spinning: refer to example 4.

And (3) post-treatment: refer to example 4.

Comparative example 3

preparing a pre-stripping dispersion of palladium powder: refer to example 4.

Preparing a mixture of palladium powder and graphene oxide: refer to example 4.

Preparing a palladium nanosheet/graphene oxide dispersion liquid: a mixture of palladium powder and graphene oxide was dispersed in DMF to prepare a mixed solution, wherein the concentration of the mixture of palladium powder and graphene oxide was as in example 4. The mixed solution was concentrated by a vacuum rotary evaporation method, and specifically, the temperature, the degree of vacuum, and the like of the vacuum rotary evaporation method (simply referred to as "rotary evaporation") were as in example 4. The solid content concentration of the concentrated mixture was as in example 4. And concentrating to obtain the palladium nanosheet/graphene oxide dispersion liquid.

Spinning: refer to example 4.

And (3) post-treatment: refer to example 4.

Effects of the embodiment

(1) Antibacterial testing

Taking the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane prepared in the examples 1 to 8 and the comparative examples 1 to 3, cutting the fiber membrane with the length, the width and the thickness of 20cm and about 0.5mm by a blade, and inserting electrodes at two ends of the fiber membrane for electrifying and generating heat and carrying out an antibacterial test. The test method is as follows: the culture solution (rejuvenated) of model strains (escherichia coli, candida albicans, salmonella typhimurium, staphylococcus aureus) was spotted by means of an inoculating needle onto petri dishes (containing conventional solid medium for bacterial culture), each petri dish was inoculated with a single strain 10 times and each strain 200 times (divided into 20 dishes). After inoculation, all the culture dishes are divided into two groups and respectively placed in two culture chambers for simulating living environment. One of them is the laboratory group culture room, is provided with a plurality of aforementioned fibrous membranes in the laboratory group culture room and circular telegram heat production, and the culture dish is 5 ~ 30cm apart from the fibrous membrane, and the laboratory group culture room is by fibrous membrane heat production energy supply, and the temperature control in the culture room is about 37 ℃, and another culture room is the control group culture room, and the temperature that sets up the control group culture room equally is 37 ℃, is supplied heat by the air conditioner, and statistics laboratory group bacterial colony growth condition after 12h all cultivateed in laboratory group culture room and control group culture room. The average colony size (diameter of colony) of each bacterial colony in the control group is calculated, the average colony size is used as a reference value, the colony with the diameter less than or equal to half of the reference value in the experimental group is marked as bacteriostasis, the colony which does not grow at the point of sample application is marked as sterilization, and the colony with the diameter more than or equal to half of the reference value is marked as normal growth. The results of the statistical percentages are shown in Table 6.

TABLE 6 antimicrobial test results

From the results in table 6, it is clear that the palladium nanosheet/graphene-based fiber membranes prepared in examples 1-8 all showed over 99% of bactericidal rate against escherichia coli, candida albicans, and salmonella typhimurium, and over 91% of bactericidal rate against staphylococcus aureus after being electrified. After the palladium nanosheets and the graphene are mutually doped, the palladium nanosheets and the graphene can be promoted to be directly contacted and doped, the palladium nanosheets or the graphene are prevented from being stacked or partially gathered, the spinnability of a single two-dimensional material spinning solution can be improved, the palladium nanosheets and the graphene are mixed with dispersed carbon black powder, the mutually doped palladium nanosheets and the graphene are directly adsorbed on the carbon black powder, a stable conductive network structure of palladium nanosheets-graphene-carbon black particles can be formed, meanwhile, the palladium nanosheets or graphene layers are prevented from being stacked mutually or easily faulted (partially broken circuit) under the action of external force, the number of conductive network channels is increased, the resistance is reduced, the structure of a conductive network is perfected, and the conductive performance and the long-term stability of the palladium nanosheet/graphene-based fiber membrane are improved. After the palladium nanosheet/graphene-based fiber membrane is electrified, the surface area can be increased by virtue of a large number of void structures existing on the surface of the fiber membrane, the palladium nanosheet-graphene-carbon black particles are facilitated to release a large number of infrared rays, and the sterilization effect is achieved. In addition, by means of carrier transmission between the palladium nanosheet and the graphene sheet layer, a small amount of active oxygen free radicals can be generated at the heterojunction between the palladium nanosheet and the graphene sheet layer, and the effects of assisting sterilization and cleaning the surface are achieved.

In contrast, the graphene-based fiber membrane prepared in comparative example 1 has a sterilization rate of 80% for escherichia coli, candida albicans, and salmonella typhimurium and a sterilization rate of 67% for staphylococcus aureus after being electrified. The reason may be related to that the graphene-based fiber film prepared in comparative example 1 has a relatively low infrared emissivity, and the graphene-based fiber film prepared in comparative example 1 only contains electric conductors such as graphene and carbon black, and lacks the auxiliary effect of palladium nanosheets, so that the graphene-based fiber film has a relatively low infrared emissivity and cannot generate active radicals. The palladium nanosheet/graphene-based fiber membrane prepared in the comparative example 2 has the sterilization rate of 93% for escherichia coli, candida albicans and salmonella typhimurium and only 83% for staphylococcus aureus after being electrified. Based on the fact that sufficient water bath ultrasound is not performed in comparative example 2, graphene oxide is directly added into the pre-stripping dispersion liquid of palladium powder, the palladium nanosheet can not be stripped with the assistance of graphene, and an effective palladium nanosheet/graphene mutual doping structure can not be formed, so that the prepared palladium nanosheet/graphene-based fiber membrane active conductor has the defects of nonuniform dispersion, low infrared emissivity, low yield of active free radicals, low antibacterial efficiency and the like. The palladium nanosheet/graphene-based fiber membrane prepared in the comparative example 3 has the sterilization rate of 92% on escherichia coli, candida albicans and salmonella typhimurium and the sterilization rate of 79% on staphylococcus aureus after being electrified. As with comparative example 2, based on that pulse probe ultrasound is not performed in comparative example 3, the palladium nanosheet cannot be peeled off with the aid of graphene, and an effective palladium nanosheet/graphene mutual doping structure cannot be formed, resulting in the defects of uneven dispersion, low infrared emissivity, low yield of active free radicals, low antibacterial efficiency and the like of the prepared palladium nanosheet/graphene-based fiber membrane active conductor.

(2) Infrared wavelength and normal emissivity testing

The palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane prepared in the examples 1 to 8 and the comparative examples 1 to 3 is used for testing the infrared wavelength and the normal emissivity according to the health care function textile of CAS 115-. The calculation data show that the palladium nanosheet/graphene-based fiber membrane prepared in the embodiment 1-8 can release far infrared rays of 3-20 micrometers, the proportion of the far infrared rays in a 4-16 micrometer waveband is over 88%, the normal emissivity is over 90%, and the increase of the microcirculation blood flow of animal experiments is over 69%. The electrothermal conversion rate is up to more than 99%, and the visible heating film can be widely applied to the fields of floor heating, physical therapy, clothes and the like. In contrast, the ratio of far infrared rays in the 4-16 micron wavelength band of the palladium nanosheet/graphene-based fibrous membrane or the graphene-based fibrous membrane prepared in comparative examples 1-3 is less than 75% (67% for the graphene-based fibrous membrane in example 1), the normal emissivity is less than 81% (67% for the graphene-based fibrous membrane in example 1), and the increase in the animal experimental microcirculation blood flow is less than 64% (50% for the graphene-based fibrous membrane in example 1). The reason for this is probably related to the stable circuit network structure formed by the palladium nanosheet/graphene-based fiber membrane, i.e., the palladium nanosheet and the graphene are doped with each other, so that the uniform distribution of the electric conductor is increased, the resistance value of the fiber membrane is reduced, the uniformity of the spinning fiber is improved, and the like.

(3) Stability and leakage safety testing

Taking the palladium nanosheet/graphene-based fiber film or the graphene-based fiber film prepared in the examples 1 to 8 and the comparative examples 1 to 3, cutting the fiber film with the length, the width and the thickness of 20cm and about 0.5mm by a blade, inserting electrodes at two ends of the fiber film, connecting a mains supply to the palladium nanosheet/graphene-based fiber film or the graphene-based fiber film to generate heat, and assessing the uniformity of heating temperature by an infrared imaging instrument. The heating temperature difference of any two positions of each fiber membrane is less than or equal to 5 ℃ and more than 2.5 ℃, the fiber membrane is marked as qualified, the fiber membrane is less than or equal to 2.5 ℃, the fiber membrane is marked as excellent, the fiber membrane is marked as unqualified when the temperature is more than 5 ℃, and the statistical result is shown in table 7.

And continuously electrifying the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane for heat generation uniformity test to generate heat for heat generation stability test. The statistical method, the heat production is carried out for 90000 hours by continuous electrification, and compared with the beginning of the heat production, the disqualification is marked when the heat production power is reduced by more than 2.5 percent after the 90000 hours of the heat production; the heat production power is reduced by less than or equal to 2.5 percent and is greater than 1 percent, and the product is marked as qualified; the decrease of heat generation power less than or equal to 1% is marked as excellent, and the statistical results are shown in Table 7.

The two surfaces of the composite palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane are hot-pressed by adopting an insulating polymer membrane (such as PET or PI), and the power is continuously electrified to generate heat for 90000 hours after the power is electrified so as to be used for a leakage safety test. The specific test method was measured with reference to GB/T12113 (idt IEC 60990). The leakage current is less than or equal to 0.05mA and greater than 0.02mA and is marked as qualified; the leakage current is less than 0.02mA and is marked as excellent; the leakage current is greater than 0.05mA and is marked as unqualified. The measurement results are shown in Table 7.

TABLE 7 stability and leakage safety test results

As can be seen from the results in table 7, most of the palladium nanosheet/graphene-based fibrous membranes prepared in examples 1 to 8 showed excellent test results in the temperature uniformity test, the heat generation stability test and the leakage safety test, and only example 1 showed a qualified test result, which indicates that the palladium nanosheet/graphene-based fibrous membranes prepared in examples 1 to 8 of the present invention have excellent heat generation uniformity, heat generation stability and leakage safety. The fiber films prepared in the comparative example 1 are unqualified in temperature uniformity test and heat generation stability test, and the fiber films prepared in the comparative examples 2 and 3 are qualified in temperature uniformity test and heat generation stability, and may be related to uneven dispersion of the conductor, unstable conductor and easy aging under the condition of electrifying.

(4) Sheet resistance test

Taking the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane prepared in the examples 1 to 8 and the comparative examples 1 to 3, cutting the fiber membrane with the length, the width and the thickness of 20cm and about 0.5mm by a blade, inserting electrodes at two ends of the fiber membrane, connecting a mains supply to the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane for heat generation, and carrying out a sheet resistance test. The test method is as follows: continuously electrifying the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane to generate heat, and testing the sheet resistance value of the graphene fiber membrane once every other week (W). The test results are shown in Table 8.

TABLE 8 sheet resistance test results

As can be seen from the results in table 8, the sheet resistance of the palladium nanosheet/graphene-based fiber membranes prepared in examples 1 to 8 is small (no more than 350 Ω/□), the variation of the sheet resistance is not obvious around when heat is generated by continuous energization, and both the sheet resistance and the stability thereof are suitable for being applied to electric heating equipment and can be widely applied to the fields of floor heating, physiotherapy, clothing and the like. In contrast, the palladium nanosheet/graphene-based fibrous membrane or graphene-based fibrous membrane prepared in comparative examples 1-3 has a large initial sheet resistance (the sheet resistance value after stabilization is still large and may be related to instability and easy aging of the fibrous membrane component under the condition of electrification and heat generation), a large change in sheet resistance value, a significant decrease in heat generation power, and is not suitable for being applied to electric heating equipment. The reason for this is that the dispersion of the electrical conductor such as palladium nanosheets and graphene may be uneven.

(5) Heat resistance and tensile Property test

Taking the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane prepared in the examples 1-8 and the comparative examples 1-3, cutting the fiber membrane with the blade, wherein the fiber membrane is 20cm long and wide and about 0.5mm thick, and carrying out a thermal deformation temperature test according to GB/T1634-2004, wherein the heating rate is 120 ℃/h. The test results are shown in Table 9.

The prepared palladium nanosheet/graphene-based fiber membrane or graphene-based fiber membrane is taken to be subjected to tensile resistance test on a universal tester (the test standard is GB/T1040-.

TABLE 9 Heat resistance test results

From the results in table 9, it can be seen that the thermal deformation temperatures of the palladium nanosheet/graphene-based fibrous membrane or the graphene-based fibrous membrane prepared in examples 1 to 8 and comparative examples 1 to 3 both exceed 98 ℃, and the fibrous membrane can meet the heat generation requirements of low-temperature and medium-high-temperature heat-generating equipment. The heat distortion temperature is related to the PAN content in the palladium nanosheet/graphene-based fibrous membrane or the graphene-based fibrous membrane. Within a certain range, the thermal deformation temperature of the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane is increased along with the increase of the PAN content, and the good dispersion of the palladium nanosheet and the graphene is also beneficial to the increase of the thermal deformation temperature; however, too high a PAN content results in a dope that is too viscous and affects spinnability and fiber porosity.

From the results in table 9, it is known that the tensile strength of the palladium nanosheet/graphene-based fiber film or the graphene-based fiber film prepared in examples 1 to 8 and comparative examples 1 to 3 exceeds 20MPa, and the requirements of flexibility, wear resistance and tensile resistance of common heat-generating equipment can be met. The tensile strength of the fiber membrane is related to the content of PAN (polyacrylonitrile), within a certain range, the tensile strength of the palladium nanosheet/graphene-based fiber membrane or the graphene-based fiber membrane is improved along with the improvement of the content of PAN, and the good dispersion of the palladium nanosheet and graphene is also beneficial to improving the tensile strength.

(6) Test of photothermal conversion Property

The palladium nanosheet/graphene-based fiber film or the graphene-based fiber film prepared in example 4 and comparative examples 1 to 3 is cut into fiber films with the length, the width and the thickness of each fiber film being 20cm and about 0.5mm by a blade, the four fiber films are placed in an illumination box (the ambient temperature is 20 ℃) provided with a 35W HD xenon lamp (simulated sunlight), the distance between the four fiber films and the HD xenon lamp is 20cm, and the temperature change of the fiber films along with the extension of illumination time is tested by a temperature sensor. The test results are shown in FIG. 7.

From the results in fig. 7, it is clear that the palladium nanosheet/graphene-based fiber membrane prepared in example 4 can be rapidly heated to 67 ℃ after being irradiated with light for one minute, and can be heated to about 83 ℃ by continuous irradiation with light. The graphene-based fiber membrane prepared in comparative example 1 can be heated to 47 ℃ after being irradiated by light for one minute, and can be heated to about 66 ℃ by continuous irradiation. The palladium nanosheet/graphene-based fiber membrane prepared in comparative example 2 can be heated to 61 ℃ after being irradiated for one minute, and can be heated to about 78 ℃ by continuous irradiation. The palladium nanosheet/graphene-based fiber membrane prepared in comparative example 3 can be heated to 54 ℃ after being irradiated for one minute, and can be heated to about 75 ℃ by continuous irradiation. Therefore, the palladium nanosheet/graphene-based fiber membrane has the advantages of remarkable photothermal effect and high photo-thermal efficiency, can generate heat by utilizing solar energy when being applied to the fields of floor heating, physiotherapy and clothes, integrates the heat generation of electricity and the heat generation of heat of light, is convenient for users to use, and is energy-saving and environment-friendly.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A palladium nanosheet/graphene-based traditional Chinese medicine hot compress device is characterized by comprising a hot compress sleeve and a palladium nanosheet/graphene-based heating film, wherein a first containing bag is arranged on the outer side of the hot compress sleeve and used for containing the palladium nanosheet/graphene-based heating film, a second containing bag is arranged on the inner side of the hot compress sleeve and used for containing a traditional Chinese medicine bag;

2. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 1, wherein a transparent sheet layer is disposed on an outer side of the hot compress sleeve, and the transparent sheet layer and an outer surface of the hot compress sleeve enclose to form a first containing bag.

3. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 1, wherein a barrier layer is disposed on an inner side of the hot compress sleeve, a porous sheet layer is disposed on a side of the barrier layer facing away from the hot compress sleeve, and the porous sheet layer and the barrier layer enclose a second containing bag.

4. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 3, wherein a sealing ring is further disposed on a side of the barrier layer facing away from the hot compress sleeve, the sealing ring being disposed around the second receiving bag;

the cross section of the sealing ring is arranged to be concave.

5. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 3, further comprising a steam discharge pipe and a pressure limiting valve, wherein the steam discharge pipe penetrates through the sealing ring and is used for discharging steam inside the sealing ring;

the pressure limiting valve is arranged on the steam discharge pipe and used for controlling the air pressure inside the sealing ring.

6. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 1, wherein a male buckle is arranged at one end of the hot compress sleeve, and a female buckle is arranged at the other end of the hot compress sleeve;

the traditional Chinese medicine bag is made of sponge materials, and an opening capable of being opened and closed is formed in one side of the traditional Chinese medicine bag.

7. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 1, wherein a transparent heat conducting layer is further disposed between the second transparent insulating layer and the palladium nanosheet/graphene-based fibrous membrane.

8. The palladium nanosheet/graphene-based traditional Chinese medicine hot compress device of claim 7, wherein a waterproof adhesive layer is further disposed between the first transparent insulating layer and the second transparent insulating layer, and the waterproof adhesive layer is respectively adhered to the first transparent insulating layer and the second transparent insulating layer to form a closed cavity;

the palladium nanosheet/graphene-based fiber membrane and the transparent heat conduction layer are both arranged in the closed cavity, and the electrode extends out of the closed cavity.

9. The palladium nanoplate/graphene-based traditional Chinese medicine hot compress device of claim 8, further comprising a heat reflecting layer, wherein the heat reflecting layer is configured in a concave shape to form a receiving groove;

the first transparent insulating layer and the palladium nanosheet/graphene-based fiber membrane are arranged in the accommodating groove.

10. The palladium nanoplate/graphene-based traditional Chinese medicine hot compress device of claim 9, wherein the heat reflecting layer comprises a reflecting film and an insulating film, the reflecting film coating an outer surface of the insulating film;

the insulating film is equipped with the flange towards the one end of second transparent insulation layer, be equipped with the draw-in groove that is used for the holding flange on the periphery wall of waterproof adhesive linkage.