CN111210998B - 3D multifunctional flexible material and application thereof - Google Patents
3D multifunctional flexible material and application thereof Download PDFInfo
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- CN111210998B CN111210998B CN202010115768.9A CN202010115768A CN111210998B CN 111210998 B CN111210998 B CN 111210998B CN 202010115768 A CN202010115768 A CN 202010115768A CN 111210998 B CN111210998 B CN 111210998B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a 3D multifunctional flexible material and application thereof, wherein the flexible material comprises a substrate layer, an interface anchoring layer wrapped outside the substrate layer and a conduction adsorption layer growing on the interface anchoring layer; the flexible material can be used for preparing flexible all-solid-state supercapacitors, flexible thermal resistance heaters and wearable self-heating flexible energy storage devices. The positive electrode and the negative electrode of the flexible all-solid-state supercapacitor are both made of a 3D multifunctional flexible material; the flexible thermal resistance heater is made of a 3D multifunctional flexible material; the wearable self-heating flexible energy storage device comprises a flexible all-solid-state supercapacitor, a lead and a flexible thermal resistance heater. The flexible all-solid-state supercapacitor disclosed by the invention has high energy density and excellent cycle stability; the flexible thermal resistance heater only needs a small voltage to have a high saturation temperature; the wearable self-heating flexible energy storage device can have good saturation temperature under very low voltage, and can be used for warm keeping, thermal therapy and the like.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a 3D multifunctional flexible material and application thereof.
Background
Human beings have caused serious environmental problem and energy crisis to fossil energy's transition dependence and consumption, for realizing the development and the utilization of sustainable development's energy, new forms of energy and novel energy device research arouse extensive concern. A super capacitor is an energy storage device, has very high power density, long cycle life, high charging and discharging speed, no pollution to the environment and the like, and is widely applied to the fields of aerospace, communication equipment, standby power supplies, national defense science and technology, electric automobiles and the like which concern the lives of people in society.
Due to obesity, various occupational diseases or aging, the joints of the human body are easy to be injured. While joint injuries often result in a number of symptoms such as pain, swelling and muscle weakness, heat therapy is widely used to ameliorate these symptoms. Heat therapy is one of the classic orthopedic treatments, commonly used for the treatment of rheumatoid arthritis, cervical spondylosis and trauma. The widespread use of mobile consumer devices and flexible wearable devices continues to require the development of more portable energy storage devices with superior cycling stability. Therefore, there is a need for a wearable self-heating flexible energy storage device which is convenient to wear, movable to use, portable and capable of circularly and stably storing energy, so as to meet the requirements of people in thermal therapy and warm keeping.
The extensive research of nano materials greatly promotes the vigorous development of advanced energy storage technologies such as super capacitors and the like. The carbon nano tube is applied to the research of electrode materials of the super capacitor due to the fact that the carbon nano tube is rich in earth storage, high in electrical conductivity and thermal conductivity, large in specific surface area and good in acid and alkali resistance. However, the common problems in the field of nano materials, such as poor conductivity, nonuniform local dispersion, unstable performance of the contact surface of the electrode material with electrolyte, and the like, exist in the electrode material of the super capacitor, and the basic performance of the super capacitor is influenced. The electrode material structure determines the performance of the device, such as flexibility, high specific capacity, high stability and the like. The design of the synthetic electrode needs to consider parameters such as active components, a loading mode, a specific surface area and the like, optimize the electrode structure and realize the construction of a high-performance device. Therefore, the design, synthesis and performance research of the electrode material of the super capacitor are very important.
Disclosure of Invention
In view of the above prior art, the present invention aims to provide a 3D multifunctional flexible material and applications thereof. The 3D multifunctional flexible material disclosed by the invention realizes the construction of active components, anchoring load and a three-dimensional flexible electrode with a large specific surface area in one step, and has an obvious effect when being used in a flexible all-solid-state supercapacitor or a flexible resistance heater.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a 3D multifunctional flexible material is provided, which includes a substrate layer, an interface anchoring layer wrapped outside the substrate layer, and a conductive adsorption layer grown on the interface anchoring layer;
the substrate layer is one of carbon cloth, graphite paper or metal foil;
the interface anchoring layer is molybdenum carbide particles;
the conductive adsorption layer is a carbon nano tube;
the carbon nano tube is vertically grown on the molybdenum carbide particles; the top end of the carbon nano tube is coated with metal nano particles, and the carbon nano tube is also modified with molybdenum carbide nanoclusters.
Preferably, the metal nanoparticles are one of nickel nanoparticles, cobalt nanoparticles, iron nanoparticles, or copper nanoparticles.
Preferably, the diameter of the carbon nano tube is 20-100 nm; the diameter of the metal nanoparticles is 20-60 nm; the diameter of the molybdenum carbide nanocluster is 2-10 nm; the diameter of the molybdenum carbide particles is 10-50 nm.
In a second aspect of the invention, there is provided a use of a 3D multifunctional flexible material in at least one of the following 1) to 3):
1) preparing a flexible all-solid-state supercapacitor;
2) preparing a flexible thermal resistance heater;
3) and preparing the wearable self-heating flexible energy storage device.
In a third aspect of the invention, a flexible all-solid-state supercapacitor is provided, which comprises a positive electrode and a negative electrode;
the positive electrode and the negative electrode are both made of 3D multifunctional flexible materials.
In a fourth aspect of the invention, a flexible thermal resistance heater is provided, which is made of a 3D multifunctional flexible material.
In a fifth aspect of the invention, a wearable self-heating flexible energy storage device is provided, and the wearable self-heating flexible energy storage device comprises a flexible all-solid-state supercapacitor, two ends of the flexible all-solid-state supercapacitor are respectively connected with a first lead and a second lead, and the other ends of the first lead and the second lead are connected with a flexible thermal resistance heater.
Preferably, the first lead and the second lead are both one of a rubber belt, a silica gel belt or a plastic belt for wrapping copper leads; and a switch is arranged on the first lead.
Preferably, wire adjustment shrinkers are arranged on the first wire and the second wire, and the second wire is connected with the flexible thermal resistance heater through magnetic attraction type contacts.
In a sixth aspect of the invention, there is provided the use of a wearable self-heating flexible energy storage device for thermal therapy and warming.
The invention has the beneficial effects that:
1. the 3D multifunctional flexible material disclosed by the invention is regular in appearance, uniform in distribution, high in specific surface area and good in conductivity. The composite 3D electrode consisting of the carbon nano tube, the metallic nickel and the molybdenum carbide is obtained through high-temperature carbonization, and the preparation process is simple.
2. According to the 3D multifunctional flexible material, different components have different functions, and have good synergistic effect with each other, so that the material can be used as a positive electrode and a negative electrode of a super capacitor, and has good electrochemical performance and cycle life; the electric heating device can also be used as a thermal resistance heater, has good saturation temperature under very low voltage, and provides heat for human bodies.
3. The flexible all-solid-state supercapacitor provided by the invention has high energy density and excellent cycle stability.
4. The flexible thermal resistance heater of the invention has very high saturation temperature only by needing very small voltage, and the surface temperature of the flexible thermal resistance heater is uniform.
5. The wearable self-heating flexible energy storage device can have good saturation temperature under low voltage, can be used for wearable heat preservation, thermal therapy and the like, and provides heat for the thermal therapy.
Drawings
FIG. 1: the structure diagram of the 3D multifunctional flexible material is shown, wherein 1 is carbon fiber, 2 is molybdenum carbide particles, 3 is carbon nanotubes, 4 is nickel nanoparticles, and 5 is molybdenum carbide nanoclusters.
FIG. 2: XRD pattern of the 3D multifunctional flexible material.
FIG. 3: SEM pictures of 3D multifunctional flexible material, wherein picture (a) is magnified to 2 μm and picture (b) is magnified to 300 nm.
FIG. 4: (a) is SEM image of the cross section of the 3D multifunctional flexible material, and (b) is enlarged view in the box of FIG. 4(a), wherein 1 is carbon fiber, 2 is an interface anchoring layer composed of molybdenum carbide particles, and 3 is a carbon-coated nickel nanotube array.
FIG. 5: the wearable self-heating flexible energy storage device comprises a wearable self-heating flexible energy storage device, wherein 1 is a flexible all-solid-state supercapacitor, 2 is a flexible thermal resistance heater, 3 is a first lead, 4 is a second lead, 5 is a switch, and 6 is a lead adjustment contractor.
FIG. 6: a heating time-temperature curve diagram of the wearable self-heating flexible energy storage device.
FIG. 7: time-temperature curves of the 3D multifunctional flexible material under different direct current voltages and corresponding saturation temperature thermal imaging graphs.
FIG. 8: cyclic voltammograms at different scan speeds,
wherein, (a) is a cyclic voltammetry curve of a 3D multifunctional flexible material as a cathode at different scanning speeds;
(b) the method is characterized in that a 3D multifunctional flexible material is used as a cyclic voltammetry curve of a positive electrode at different scanning speeds;
(c) the cyclic voltammetry curve of a 3D multifunctional flexible material as a positive electrode and a negative electrode at the same scanning speed
(d) The cyclic voltammetry curves of the flexible all-solid-state supercapacitor made of the 3D multifunctional flexible material at different scanning speeds.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background art, the super capacitor manufactured by the existing flexible electrode has the problems of poor conductivity, uneven local dispersion, unstable performance of the contact surface of the super capacitor and the electrolyte, and the like, and the preparation process of the flexible material is complex. Based on the structure, the invention provides a 3D multifunctional flexible material which is formed by a substrate layer, an interface anchoring layer and a conduction adsorption layer, has a sandwich-like 3D structure (shown in figure 1), is regular in appearance, uniform in distribution, high in specific surface area and good in conductivity.
The 3D multifunctional flexible material can be prepared by the following steps:
(1) dissolving sodium molybdate and nickel chloride in distilled water to obtain light blue clear sodium molybdate-nickel chloride mixed solution;
(2) immersing the carbon cloth into the sodium molybdate-nickel chloride mixed solution obtained in the step (1), transferring the mixture into a closed container, drying the closed container at 160 ℃ for 6 hours, taking out the carbon cloth, cleaning and drying to obtain the carbon cloth (namely NiMoO) loaded with the nickel molybdate nano-sheets4/CC)；
(3) And (3) mixing and sealing the carbon cloth loaded with the nickel molybdate nanosheets obtained in the step (2) with dicyandiamide, and calcining under the protection of inert gas to obtain the 3D multifunctional flexible material, namely MoC/Ni @ NCNTs/CC.
In the step (1), the molar ratio of the sodium molybdate to the nickel chloride is 1: 1.
In the step (3), the mass ratio of the dicyandiamide to the carbon cloth loaded with the nickel molybdate nanosheets is 20: 1-40: 1.
In the step (3), the inert gas is argon.
In the step (3), the calcining temperature is 700-800 ℃, the heating rate is 2-5 ℃/min, the inert gas flow rate is 20-60 mL/min, and the calcining time is 1-3 h.
According to the method, sodium molybdate and nickel chloride can be added in one-step reaction, and meanwhile, a nano molybdenum carbide particle interface anchoring layer, a carbon-coated nickel nanotube and a modified molybdenum carbide nanocluster on the carbon nanotube are formed (as shown in fig. 4). The preparation process is simple, the prepared 3D multifunctional flexible material takes the carbon cloth as a substrate layer, the molybdenum carbide particles are wrapped on the carbon fibers of the carbon cloth to form an interface anchoring layer, the stability of an electrode interface is improved, the carbon nano tube is used as an active component of a cathode of a super capacitor, has a large specific surface area, adsorbs a large number of electrolyte ions, provides more double electric layer capacitance, has excellent conductivity and heat transfer performance, and can be used as a conductive layer for conducting electrons. The molybdenum carbide nanoclusters further increase the specific surface area of the material, increase the capacitance, and can improve the conductivity. The nickel is used as a main active component of the positive electrode of the super capacitor and performs a rapid and reversible oxidation-reduction reaction with ions in the electrolyte, so that a high specific capacitance value is provided. All the components cooperate with each other to improve the electronic conduction performance and the electrochemical performance of the 3D multifunctional flexible material together.
Besides preparing the flexible all-solid-state supercapacitor, the 3D multifunctional flexible material can also be used for preparing a flexible thermal resistance heater and a wearable self-heating flexible energy storage device. The wearable self-heating flexible energy storage device comprises a flexible all-solid-state supercapacitor, two ends of the flexible all-solid-state supercapacitor are respectively connected with a first lead and a second lead, and the other ends of the first lead and the second lead are connected with a flexible thermal resistance heater (see fig. 5).
When the 3D multifunctional flexible material is used as a flexible electrode to prepare a flexible all-solid-state supercapacitor, PVA/KOH is used as a solid electrolyte, and the 3D multifunctional flexible material is used as a positive electrode and a negative electrode to assemble the flexible all-solid-state supercapacitor. The 3D multifunctional flexible material used as the flexible electrode for preparing the flexible all-solid-state supercapacitor benefits from the synergistic effect of the high conductivity, the high surface area, the nickel coated by the carbon nano tube and each component.
When the 3D multifunctional flexible material is used as the flexible thermal resistance heater, the positive and negative leads of the direct current power supply are respectively clamped at two ends of the 3D multifunctional flexible material, the direct current power supply is switched on, voltage is applied, electrons move towards a place where the electric potential rises to collide with atoms and molecules under the action of an electric field to generate heat energy after certain voltage is applied to the two ends of the flexible material based on the principle of Joule heat, the smaller the resistance of the flexible material is, the larger the current flowing under constant voltage is, the more the electrons pass through, and the faster the generated heat is. As the voltage increases, the more current flows and the higher the saturation temperature is reached, without the resistance of the flexible material changing. The molybdenum carbide particles on the interface anchoring layer improve the electronic conductivity to generate more heat, and the carbon nano tube has good conductivity and heat transfer performance, so that the saturation temperature of the whole material can be greatly improved.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Example 1
71mg (0.3mmol) of nickel chloride hexahydrate and 72mg (0.3mmol) of sodium molybdate dihydrate are weighed, poured into a beaker, added with 30mL of distilled water, stirred to dissolve the solute, then transferred into a 50mL high-pressure reaction kettle, and put into a 1 x 2cm piece of clean carbon cloth in solution. And (3) carrying out temperature programming at 5 ℃/min in a forced air drying oven, carrying out heat preservation at 160 ℃ for 6h, taking out the carbon cloth in the reaction kettle after cooling, cleaning, and then carrying out vacuum drying at 60 ℃ for 8h to obtain the precursor.
And putting the obtained precursor and 20mg of dicyandiamide into a porcelain boat, sealing the porcelain boat by using copper foil, putting the porcelain boat into a tube furnace, raising the temperature by 5 ℃/min in Ar atmosphere, keeping the temperature at 750 ℃ for 2h, keeping the pressure at normal pressure and the flow rate at 30mL/min to obtain the 3D multifunctional flexible material.
XRD and SEM tests are respectively carried out on the 3D multifunctional flexible material, and the obtained results are shown in figures 2, 3 and 4.
Example 2
120.9mg (0.5mmol) of nickel chloride hexahydrate and 118.8mg (0.5mmol) of sodium molybdate dihydrate were weighed, poured into a beaker, added with 30mL of distilled water, stirred to dissolve the solute, and then transferred to a 50mL autoclave, into which 1X 2cm of clean carbon cloth was put. And (3) carrying out temperature programming in a forced air drying oven at 3 ℃/min, carrying out heat preservation at 160 ℃ for 6h, taking out the carbon cloth in the reaction kettle after cooling, cleaning, and then carrying out vacuum drying at 60 ℃ for 12h to obtain the precursor.
Putting the obtained precursor and 30mg dicyandiamide into a porcelain boat, sealing the porcelain boat by using copper foil, putting the porcelain boat into a tube furnace, sequentially heating the porcelain boat and the dicyandiamide at the temperature of 700 ℃ for 5 ℃/min in a nitrogen atmosphere, and keeping the porcelain boat and the dicyandiamide at the temperature of 700 ℃ for 3h at normal pressure at the flow rate of 20 mL/min.
Example 3
As shown in fig. 5, the wearable self-heating flexible energy storage device includes a flexible all-solid-state supercapacitor 1, two ends of the flexible all-solid-state supercapacitor 1 are respectively connected to a first conducting wire 3 and a second conducting wire 4, and the other ends of the first conducting wire 3 and the second conducting wire 4 are connected to a flexible thermal resistance heater 2.
The first lead 3 and the second lead 4 are both rubber belts, silica gel belts or plastic belts for coating copper leads; the first conducting wire 3 is provided with a switch 5.
When the wearable self-heating flexible energy storage device is used, the lengths of the first lead 3 and the second lead 4 can be adjusted according to the size of a used part, and the second lead 4 and the flexible thermal resistance heater 2 are connected together through a magnetic attraction type contact. The switch 5 on the first conducting wire 3 is turned on, the flexible thermal resistance heater 2 generates heat, and the heat therapy is started. After the heat treatment is finished, the switch 5 is closed, the second lead 4 and the flexible thermal resistance heater 2 are pulled forcefully to be separated, and the wearable self-heating flexible energy storage device is folded.
Application example 1: application of 3D multifunctional flexible material as negative electrode of flexible all-solid-state supercapacitor
The electrochemical performance of the electrode was tested in 3M KOH aqueous solution as electrolyte using a three-electrode electrochemical workstation, the 3D multifunctional flexible material prepared in example 1 as working electrode, Pt sheet (5mm × 5mm × 0.1mm) as counter electrode, Hg/HgO electrode as reference electrode.
The 3D multifunctional flexible material is used as a negative electrode, and has enhanced specific capacitance (at 10mV s)-1Specific time capacitance of 338mF cm-2) Rate capability (at 200mV s)-1Specific time capacitance of 262mF cm-2) And the capacitor can still keep 95.3% of the initial value after 8000 cycles of charging and discharging. The cyclic voltammogram results at different scan speeds are shown in fig. 8 (a).
Application example 2: application of 3D multifunctional flexible material as positive electrode of flexible all-solid-state supercapacitor
The electrochemical performance of the electrode was tested in 3M KOH aqueous solution as electrolyte using a three-electrode electrochemical workstation, the 3D multifunctional flexible material prepared in example 2 as working electrode, Pt sheet (5mm × 5mm × 0.1mm) as counter electrode, Hg/HgO electrode as reference electrode.
As the anode, the flexible material is in 5mV s-1Shows 1210mF cm-2And also after 6000 consecutive cycles, 95.7% of the initial capacitance, indicating a very good stability of the material. The result of the cyclic voltammetry curve of the anode at different scanning speeds is shown in fig. 8(b), and the curve has oxidation reduction peaks with good symmetry at different scanning speeds, which also shows that the material has good stability.
Application example 3: flexible all-solid-state supercapacitor assembled by using 3D multifunctional flexible material as positive electrode and negative electrode
The electrochemical performance of the flexible all-solid-state supercapacitor was tested by using PVA/KOH as a solid electrolyte, glass fiber paper as a separator, and the 3D multifunctional flexible materials prepared in examples 1 and 2 as a positive electrode and a negative electrode, respectively. The voltage window can reach 1.5V, which means that the super capacitor has excellent energy storage performance, and the result shows that the super capacitor has high energy density (the power density is 2.4mW cm)-2When the concentration is 78.7 mu Wh cm-2) And excellent cycling stability (capacity retention of about 91% after 8000 cycles). The result of cyclic voltammetry curve of the assembled super capacitor under different scanning speeds is shown in the figure8(d)
Application example 4: 3D multifunctional flexible material as flexible thermal resistance heater
Positive and negative leads of a direct current power supply are respectively clamped at two ends of the 3D multifunctional flexible material prepared in the embodiment 1, the direct current power supply is switched on, different voltages are respectively applied, the electrifying time is about 1 minute, and then an infrared thermal imaging camera is used for recording thermal imaging of the material under the whole constant voltage.
When the DC voltage reaches 3V, the saturation temperature of the material is 173 ℃, which shows that the material has very high saturation temperature when the voltage required by the material is very small, and the flexible thermal resistance heater can be used for wearable heat preservation, thermal therapy and the like. It can be seen from fig. 7 that the temperature is uniform across the surface of the material.
Application example 5: wearable self-heating flexible energy storage device prepared from 3D multifunctional flexible material
The 3D multifunctional flexible material prepared in the embodiment 1 is used as the positive electrode and the negative electrode of the flexible all-solid-state supercapacitor, the 3D multifunctional flexible material prepared in the embodiment 2 is used as the flexible thermal resistance heater, and the wearable self-heating flexible energy storage device is assembled through a lead.
When the wearable self-heating flexible energy storage device works, positive and negative leads of a direct-current power supply are respectively clamped at two ends of an electrode, the direct-current power supply is switched on, different voltages are respectively applied, the electrifying time is about 1 minute, then an infrared thermal imaging camera is used for recording thermal imaging of the whole electrode under constant voltage, and a curve of the temperature of the flexible thermal resistance heater changing along with time is made by utilizing the thermal imaging (see figure 6). The saturation temperature of the wearable self-heating flexible energy storage device reaches about 39 ℃. And the temperature of the flexible all-solid-state supercapacitor is kept at room temperature. As shown in fig. 6, the flexible thermal resistance heater can reach the saturation temperature (39 ℃) within 23 s. It is noted that the output current of the super capacitor gradually decreases, and the corresponding time-temperature curve is different from that of the direct current power supply. Therefore, the same 3D multifunctional flexible material can be used as the positive and negative electrodes of the flexible all-solid-state supercapacitor to drive the flexible heater, which means that the heater can be driven by low voltage.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (3)
1. Use of a 3D multifunctional flexible material in at least one of the following 1) to 3):
1) preparing a flexible all-solid-state supercapacitor;
2) preparing a flexible thermal resistance heater;
the flexible material comprises a substrate layer, an interface anchoring layer wrapped outside the substrate layer and a conductive adsorption layer grown on the interface anchoring layer;
the substrate layer is one of carbon cloth, graphite paper or metal foil;
the interface anchoring layer is molybdenum carbide particles;
the conductive adsorption layer is a carbon nano tube;
the carbon nano tube is vertically grown on the molybdenum carbide particles; the top end of the carbon nano tube is coated with metal nano particles, and the carbon nano tube is also modified with molybdenum carbide nanoclusters;
the metal nanoparticles are one of nickel nanoparticles, cobalt nanoparticles, iron nanoparticles or copper nanoparticles;
the diameter of the carbon nano tube is 20-100 nm; the diameter of the metal nanoparticles is 20-60 nm; the diameter of the molybdenum carbide nanocluster is 2-10 nm; the diameter of the molybdenum carbide particles is 10-50 nm;
the 3D multifunctional flexible material is prepared by the following steps:
(1) Dissolving sodium molybdate and nickel chloride in distilled water to obtain light blue clear sodium molybdate-nickel chloride mixed solution;
(2) Immersing the carbon cloth into the sodium molybdate-nickel chloride mixed solution obtained in the step (1), transferring the mixture into a closed container, drying the closed container at 160 ℃ for 6 hours, taking out the carbon cloth, cleaning and drying the carbon cloth to obtain the carbon cloth loaded with the nickel molybdate nano-sheets,namely NiMoO4/CC；
(3) Mixing and sealing the carbon cloth loaded with the nickel molybdate nanosheets obtained in the step (2) with dicyandiamide, and calcining under the protection of inert gas to obtain a 3D multifunctional flexible material, namely MoC/Ni @ NCNTs/CC;
in the step (1), the molar ratio of the sodium molybdate to the nickel chloride is 1: 1;
in the step (3), the mass ratio of the dicyandiamide to the carbon cloth loaded with the nickel molybdate nanosheets is 20: 1-40: 1;
in the step (3), the inert gas is argon; the calcining temperature is 700-800 ℃, the heating rate is 2-5 ℃/min, the inert gas flow rate is 20-60 mL/min, and the calcining time is 1-3 h.
2. A wearable self-heating flexible energy storage device is characterized by comprising a flexible all-solid-state supercapacitor, wherein two ends of the flexible all-solid-state supercapacitor are respectively connected with a first lead and a second lead, and the other ends of the first lead and the second lead are connected with a flexible thermal resistance heater; the first lead and the second lead are both rubber belts, silica gel belts or plastic belts which cover the copper leads; a switch is arranged on the first lead; the first lead and the second lead are both provided with lead adjusting shrinkers, and the second lead is connected with the flexible thermal resistance heater through a magnetic attraction type contact;
the flexible all-solid-state supercapacitor comprises a positive electrode and a negative electrode; the positive and negative electrodes are both made of the 3D multifunctional flexible material of claim 1;
the flexible thermal resistance heater is made of the 3D multifunctional flexible material of claim 1.
3. The wearable self-heating flexible energy storage device of claim 2 for use in thermal therapy and warmth.
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| CN103393237A (en) * | 2013-08-19 | 2013-11-20 | 青岛大学 | Thermoregulation garment |
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| US10366802B2 (en) * | 2009-06-05 | 2019-07-30 | University of Pittsburgh—of the Commonwealth System of Higher Education | Compositions including nano-particles and a nano-structured support matrix and methods of preparation as reversible high capacity anodes in energy storage systems |
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