CN115410835A - Multifunctional vanadium metal organic framework-based carbon nanotube fiber and preparation method and application thereof - Google Patents
Multifunctional vanadium metal organic framework-based carbon nanotube fiber and preparation method and application thereof Download PDFInfo
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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
-
- 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
- H01G11/40—Fibres
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a multifunctional vanadium metal organic framework-based carbon nanotube fiber and a preparation method thereof, the multifunctional vanadium metal organic framework-based carbon nanotube fiber is prepared by a hydrothermal method, and the application of the fiber is provided, the fiber is annealed for multiple times respectively to obtain a positive electrode material, a negative electrode material and a catalytic material of a self-driven full-fiber integrated full-hydrolysis water electronic device.
Description
Technical Field
The invention relates to the technical field of fiber electrode preparation, in particular to a multifunctional vanadium metal organic framework-based carbon nanotube fiber and a preparation method and application thereof.
Background
With the rapid development of intelligent, miniaturized wearable and portable electronic products, multifunctional integrated micro devices are popular. In which the design of highly efficient integrated systems requires reliable and stable power supply for sustainable operation, generally speaking, the energy storage and utilization devices in the reported integrated electronic devices are mostly operated independently, wherein additional external circuits inevitably lead to volume increase, weight and energy loss. Furthermore, most conventional integrated devices are based on planar structures, are rigid and bulky, and limit applications that can be worn by the human body or integrated into textiles.
In sharp contrast, fibrous integrated devices have received much attention due to their light weight, high flexibility and wearability, and in general, can be composed of energy storage devices (i.e., supercapacitors [ SC ] and batteries) and ultra-sensitive sensors (i.e., gas, pressure and humidity sensors). More importantly, they can be easily woven into textiles to capture and monitor human physiological signals and activities, well suited for portable and wearable applications. Although both fibrous energy storage and utilization devices have made a breakthrough, it is a major challenge to use multifunctional fibers in an integrated device to simultaneously achieve energy storage and utilization.
Recently, studies have reported a number of integrated systems through individual fibers that combine various functional fibrous energy storage devices with energy utilization. For example, zhao et al (Zhao J, zhang Y, huang Y, et al. Adv Sci.2018;5 (11): 1801114.) report a fibrous integrated device by combining a printed fibrous temperature sensor with a fibrous asymmetric SC, where reduced graphene oxide and V 2 O 5 VN as temperature sensitive and electrochemically active material, respectively, however, this unit component of an integrated fibrous device requires a number of different functional materials to achieve energy storage or energy utilization. To overcome this limitation, liang et al (Liang SJ, liu B, hu W, zhou K, ang LK. Adv Energy Mater.2017;7 (3): 1601208.) demonstrated a versatile fibrous MoS 2 Base electrode, useful for energy harvesting and storage applications, but it still involves a complex synthetic process because additional active material is required to match MoS 2 A multifunctional system can be formed. In addition, in consideration of the difference in physical and chemical properties between different functional materials, there is a problem of poor compatibility when they are used in one integrated device. Therefore, it is highly desirable to design a multifunctional material that can simultaneously meet the requirements of energy storage and utilization.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multifunctional vanadium metal organic framework-based carbon nanotube fiber, so as to solve the problem that the conventional fiber cannot meet the requirements of energy collection and storage application simultaneously when an integrated electronic device is prepared.
In order to solve the problems, the invention provides a preparation method of a multifunctional vanadium metal organic framework-based carbon nanotube fiber, which comprises the following steps:
s1: adding VOSO 4 、NH 4 VO 3 Dissolving terephthalic acid in N, N-dimethylformamide, and stirring to obtain a mixed solution;
s2: transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene lining stainless steel high-pressure kettle containing nickel foam, and immersing carbon nano tube fibers;
s3: and (3) transferring the autoclave treated in the step (S2) into an oven for reaction, cooling to room temperature after the reaction is finished, and drying the product in vacuum overnight to obtain the multifunctional vanadium metal organic framework-based carbon nanotube fiber, namely the V-MOF NWs @ CNT fiber.
Preferably, in the step S1, the VOSO is 4 、NH 4 VO 3 And terephthalic acid in a molar ratio of 1; the stirring temperature is 60 ℃ and the stirring time is 8 hours.
Preferably, in the step S2, the polytetrafluoroethylene-lined stainless steel autoclave has a volume of 100mL, and the nickel foam has a volume of 4cm 2 。
Preferably, in the step S3, the temperature of the reaction is 160 ℃ and the time is 48 hours; and the operation of washing the product with ethanol for a plurality of times is also included between the cooling of the reaction end to room temperature and the drying under vacuum overnight, and the temperature of the drying under vacuum overnight is 40 ℃.
The invention aims to solve one technical problem of providing the multifunctional vanadium metal organic framework-based carbon nanotube fiber prepared by the method, so as to solve the problem that the conventional fiber cannot be integrated in an integrated device for application.
In order to solve the problems, the invention provides a multifunctional vanadium metal organic framework-based carbon nanotube fiber, which is prepared by any one of the preparation methods.
The invention also provides the multifunctional vanadium metal organic framework-based carbon nanotube fiber, wherein the application comprises applying the multifunctional vanadium metal organic framework-based carbon nanotube fiber to a self-driven full-fiber integrated full-electrolysis water electronic device so as to solve the problems that the conventional self-driven full-fiber integrated full-electrolysis water electronic device needs to adopt a plurality of different functional materials to realize energy storage and energy utilization and has poor compatibility.
The application comprises the following steps:
a1: annealing the multifunctional vanadium metal organic framework-based carbon nanotube fiber in air to obtain V 2 O 5 Nws @ cnt fibers;
a2: preparing a positive electrode material: depositing CoNi-LDH nanosheets on the part of the V obtained in the step A1 by an electrochemical deposition method 2 O 5 CoNi-LDH NSs @ V obtained on NWs @ CNT fiber 2 O 5 @ CNT fiber;
preparing a negative electrode material: adding multifunctional vanadium metal organic framework-based carbon nanotube fiber in NH 3 Performing annealing to obtain VNNWs @ CNT fibers;
preparing a catalytic material: placing the multifunctional vanadium metal organic framework-based carbon nanotube fiber and sulfur powder in a ceramic boat, placing the sulfur powder at the upstream, and annealing in argon atmosphere to obtain S-VO x Nws @ cnt fibers;
a3: preparing a quasi-solid fibrous asymmetric supercapacitor: the VN NWs @ CNT fiber and the CoNi-LDH NSs @ V prepared by the step A2 2 O 5 After the @ CNT fiber is wrapped with gel, twisting and winding to obtain the quasi-solid fibrous asymmetric supercapacitor;
preparing a fibrous piezoresistive sensor: twisting and winding four VNNWs @ CNT fibers prepared in the step A2, fixing the twisted and wound VNNWs @ CNT fibers on conductive glass by using a conductive adhesive, then uniformly covering the surface of the fixed stranded fibers with a polydimethylsiloxane prepolymer solution, and curing at 60 ℃ for 2 hours for packaging to obtain a fibrous piezoresistive sensor;
a4, preparing a self-driven full-fiber integrated full-electrolysis water electronic device:
winding the fibrous piezoresistive sensor prepared in the step A3 on the quasi-solid fibrous asymmetric supercapacitor to obtain a self-powered full-fiber integrated sensing device, and meanwhile, winding the S-VO prepared in the step A2 on the quasi-solid fibrous asymmetric supercapacitor to obtain the S-VO x The NWs @ CNT fiber is used as a catalytic material to obtain the self-driven full-fiber integrated full-electrolysis water electronic device.
Preferably, in the step A1, the annealing conditions are: the annealing temperature is 400 ℃, the annealing time is 1 hour, and the heating rate is 5 ℃/min; in the step A2, the NH 3 The conditions of the medium annealing are as follows: the annealing temperature is 750 ℃, the annealing time is 2 hours, and the heating rate is 10 ℃/min; the annealing conditions under the argon atmosphere are as follows: the temperature was raised to 300 ℃ at a ramp rate of 5 ℃/min, annealing continued for 1 hour, then the temperature was further raised to 500 ℃ and held for an additional 2 hours.
Preferably, in the step A2, the conditions of the electrochemical deposition method are as follows: at 0.05mol/L of Co (NO) 3 ) 2 ·6H 2 O and 0.05mol/L Ni (NO) 3 ) 2 ·6H 2 O was electrodeposited at room temperature as an electrolyte and measured by cyclic voltammetry for 30 cycles.
Preferably, in the step A3, the preparation method of the gel comprises: 1g of polyvinyl alcohol was dissolved in 10ml of 1mol/L KOH aqueous solution at 85 ℃ to prepare a polymer gel electrolyte, and magnetic stirring was carried out for 3 hours to obtain a gel.
Compared with the prior art, the invention has the following beneficial effects:
(1) When the fiber is applied to a self-driven full-fiber integrated full-electrolysis water electronic device, the derivative of the same material is multifunctional in the integrated device, the compatibility is good, and energy storage and utilization are realized.
(2) In the preparation method of the multifunctional vanadium metal organic framework-based carbon nanotube fiber, the V-MOF NWs @ CNT fiber is prepared by a hydrothermal method, the degree of nanowire array is high, and in application, different annealing processes are performedCan be converted into V under the condition 2 O 5 NWs @ CNT fiber, VNNWs @ CNT fiber, and S-VO x NWs @ CNT fiber.
(3) In the application of the multifunctional vanadium metal organic framework-based carbon nanotube fiber, coNi-LDH NSs @ V is used 2 O 5 NWs @ CNT fiber (CoNi layered double hydroxide nanosheet @ V) 2 O 5 NWs core/shell nanostructure) as the positive electrode, VN NWs @ cnt fiber as the negative electrode, wound fiber-like asymmetric SC (FASC) with maximum operating voltage of 1.7V and high energy density can be assembled.
(4) In the application of the multifunctional vanadium metal organic framework-based carbon nanotube fiber, a fibrous piezoresistive sensor (FPS; VNNWs @ CNT fiber is also used as a high-sensitivity material) and a self-driven full-fiber integrated fully-hydrolyzed water electronic device (FASC) are twisted together to form a fibrous integrated device, wherein the high-performance FASC can provide continuous and stable output power for the FPS.
(5)S-VO x The nws @ cnt fiber electrode exhibits excellent electrocatalytic Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), and can construct a self-driven water splitting unit together with fasts.
Drawings
Fig. 1 is a multifunctional schematic diagram of multifunctional vanadium metal organic framework-based carbon nanotube fibers and derivatives thereof.
Fig. 2 is an SEM image of the multifunctional vanadium metal organic framework-based carbon nanotube fiber.
FIG. 3 shows multifunctional vanadium metal organic framework-based carbon nanotube fibers, V 2 O 5 SEM magnified images of @ CNT fiber, VN @ CNT fiber, and S-VOx @ CNT fiber.
FIG. 4 is VN @ CNT fiber negative electrode CoNi LDH NSs @ V 2 O 5 @ CV diagram of CNT fiber positive electrode.
FIG. 5 is a performance graph of a Fibrous Piezoresistive Sensor (FPS).
FIG. 6 is S-VO x OER and HER performance plots for @ CNT fibers.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a multifunctional vanadium metal organic framework-based carbon nanotube fiber, which comprises the following steps:
s1: mixing VOSO 4 、NH 4 VO 3 Dissolving terephthalic acid in N, N-dimethylformamide, and stirring to obtain a mixed solution;
s2: transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene lining stainless steel high-pressure kettle containing nickel foam, and immersing carbon nano tube fibers;
s3: and (3) transferring the autoclave treated in the step (S2) to an oven for reaction, cooling to room temperature after the reaction is finished, and drying the product in vacuum overnight to obtain the multifunctional vanadium metal organic framework-based carbon nanotube fiber.
Preferably, in the step S1, the VOSO 4 、NH 4 VO 3 And terephthalic acid in a molar ratio of 1; the stirring temperature is 60 ℃ and the stirring time is 8 hours.
Preferably, in the step S2, the polytetrafluoroethylene-lined stainless steel autoclave has a volume of 100mL, and the nickel foam has a volume of 4cm 2 。
Preferably, in the step S3, the temperature of the reaction is 160 ℃ and the time is 48 hours; and the operation of washing the product with ethanol for a plurality of times is also included between the cooling of the reaction end to room temperature and the drying under vacuum overnight, and the temperature of the drying under vacuum overnight is 40 ℃.
The invention also provides a multifunctional vanadium metal organic framework-based carbon nanotube fiber, which is prepared by any one of the preparation methods.
The invention also provides the multifunctional vanadium metal organic framework-based carbon nanotube fiber, and the application comprises the step of applying the multifunctional vanadium metal organic framework-based carbon nanotube fiber to a self-driven full-fiber integrated full-electrolysis water electronic device.
The application comprises the following steps:
a1: annealing the multifunctional vanadium metal organic framework-based carbon nanotube fiber in air to obtain V 2 O 5 Nws @ cnt fibers;
a2: preparing a positive electrode material: depositing CoNi-LDH nanosheets on the part of the V obtained in the step A1 by an electrochemical deposition method 2 O 5 CoNi-LDH NSs @ V on NWs @ CNT fibers 2 O 5 @ CNT fiber;
preparing a negative electrode material: adding multifunctional vanadium metal organic framework-based carbon nanotube fiber in NH 3 Performing annealing to obtain VNNWs @ CNT fibers;
preparing a catalytic material: placing the multifunctional vanadium metal organic framework-based carbon nanotube fiber and sulfur powder in a ceramic boat, placing the sulfur powder at the upstream, and annealing in argon atmosphere to obtain S-VO x Nws @ cnt fibers;
a3: preparing a quasi-solid fibrous asymmetric supercapacitor: the VN NWs @ CNT fiber and the CoNi-LDH NSs @ V prepared by the step A2 2 O 5 After the @ CNT fiber is wrapped with gel, twisting and winding to obtain the quasi-solid fibrous asymmetric supercapacitor;
preparing a fibrous piezoresistive sensor: twisting and winding four VNNWs @ CNT fibers prepared in the step A2, fixing the twisted and wound VNNWs @ CNT fibers on conductive glass by using a conductive adhesive, then uniformly covering the surface of the fixed stranded fibers with a polydimethylsiloxane prepolymer solution, and curing at 60 ℃ for 2 hours for packaging to obtain a fibrous piezoresistive sensor;
a4, preparing a self-driven full-fiber integrated full-electrolysis water electronic device:
winding the fibrous piezoresistive sensor prepared in the step A3 on the quasi-solid fibrous asymmetric supercapacitor to obtain a self-powered full-fiber integrated sensing device, and meanwhile, winding the S-VO prepared in the step A2 on the quasi-solid fibrous asymmetric supercapacitor to obtain the S-VO x NWs @ CNT fiber is used as catalytic material to obtain self-driven full-fiber integrated full-electrolysis water electronic deviceAnd (3) a component.
Preferably, in the step A1, the annealing conditions are: the annealing temperature is 400 ℃, the annealing time is 1 hour, and the heating rate is 5 ℃/min; in the step A2, the NH 3 The annealing conditions are as follows: the annealing temperature is 750 ℃, the annealing time is 2 hours, and the heating rate is 10 ℃/min; the annealing conditions under the argon atmosphere are as follows: the temperature was raised to 300 ℃ at a ramp rate of 5 ℃/min, annealing continued for 1 hour, then the temperature was further raised to 500 ℃ and held for an additional 2 hours.
Preferably, in the step A2, the conditions of the electrochemical deposition method are as follows: at 0.05mol/L Co (NO) 3 ) 2 ·6H 2 O and 0.05mol/L Ni (NO) 3 ) 2 ·6H 2 O was electrodeposited at room temperature as an electrolyte and measured by cyclic voltammetry for 30 cycles.
Preferably, in the step A3, the preparation method of the gel comprises: 1g of polyvinyl alcohol was dissolved in 10ml of 1mol/L KOH aqueous solution at 85 ℃ to prepare a polymer gel electrolyte, and magnetic stirring was carried out for 3 hours to obtain a gel.
The above-described solution of the invention is explained and illustrated below with reference to the actual data:
example (b):
a preparation method of a multifunctional vanadium metal organic framework-based carbon nanotube fiber comprises the following steps:
s1: 2mmol of VOSO 4 、2mmol NH 4 VO 3 Dissolving 4mmol of terephthalic acid in 80ml of N, N-dimethylformamide, and stirring for 8 hours at the temperature of 60 ℃ to obtain a mixed solution;
s2: transferring the mixed solution obtained in the step S1 to a 100ml polytetrafluoroethylene-lined stainless steel autoclave containing nickel foam, which is filled with 4cm 2 And immersing the nickel foam into the carbon nanotube fiber;
s3: and (3) transferring the autoclave treated in the step (S2) into an oven for reaction at 160 ℃ for 48 hours, cooling to room temperature after the reaction is finished, and drying the product in vacuum overnight to obtain the multifunctional vanadium metal organic framework-based carbon nanotube fiber (V-MOF NWs @ CNT fiber).
The application of the multifunctional vanadium metal organic framework-based carbon nanotube fiber is specifically to apply the fiber to the preparation of a self-driven full-fiber integrated full-hydroelectric electronic device, different fiber materials are obtained by annealing the multifunctional vanadium metal organic framework-based carbon nanotube fiber, and the self-driven full-fiber integrated full-hydroelectric electronic device is finally obtained by controlling an annealing process and a preparation method, and the application comprises the following steps:
a1: placing the multifunctional vanadium metal organic framework-based carbon nanotube fiber in air, controlling the annealing temperature to be 400 ℃, the annealing time to be 1 hour, the heating rate to be 5 ℃/min, and annealing to obtain V 2 O 5 Nws @ cnt fibers;
a2: preparing a positive electrode material: depositing CoNi-LDH nanosheets on the part of the V obtained in the step A1 by an electrochemical deposition method 2 O 5 CoNi-LDH NSs @ V on NWs @ CNT fibers 2 O 5 @ CNT fiber, under the condition of electrochemical deposition, to contain 0.05mol/L Co (NO) 3 ) 2 ·6H 2 O and 0.05mol/L Ni (NO) 3 ) 2 ·6H 2 O as electrolyte, electrodeposition was performed at room temperature for 30 cycles by Cyclic Voltammetry (CV) measurement;
preparing a negative electrode material: placing V-MOF NWs @ CNT fibers at NH 3 Performing intermediate annealing, controlling the annealing temperature to be 750 ℃, annealing for 2 hours, and heating up at a rate of 10 ℃/min to obtain VNNWs @ CNT fibers;
preparing a catalytic material: placing the V-MOF NWs @ CNT fiber prepared in the step S3 and sulfur powder in a ceramic boat, placing the sulfur powder at the upstream, annealing to 300 ℃ at a heating rate of 5 ℃/min under an argon atmosphere for 1 hour, then further raising the temperature to 500 ℃, keeping for 2 hours, and obtaining S-VO after treatment x Nws @ cnt fibers;
a3: preparing a quasi-solid fibrous asymmetric supercapacitor: wrapping the VNNWs @ CNT fiber and the CoNi-LDH NSs @ V2O5@ CNT fiber prepared in the step A2 with gel, and twisting to obtain the quasi-solid fibrous asymmetric super-asymmetric CNT fiberA stage capacitor; the preparation process of the gel is that 1g of polyvinyl alcohol (PVA) is dissolved in 10ml of 10 mol/L KOH aqueous solution to prepare polymer gel electrolyte, the preparation temperature is 85 ℃, and the polymer gel electrolyte is magnetically stirred for 3 hours; after evaporation of excess water, VNNWs @ CNT fibers and CoNi-LDH NSs @ V were coated with a gel electrolyte 2 O 5 @ surface of CNT fiber.
Preparing a fibrous piezoresistive sensor: twisting and winding four VNNWs @ CNT fibers prepared in the step A2, fixing the twisted and wound VNNWs @ CNT fibers on conductive glass by using a conductive adhesive, then uniformly covering the surface of the fixed stranded fibers with a polydimethylsiloxane prepolymer solution, and curing for 2 hours at 60 ℃ for packaging to obtain the fibrous piezoresistive sensor;
a4, preparing a self-driven full-fiber integrated full-electrolysis water electronic device:
winding the fibrous piezoresistive sensor prepared in the step A3 on the quasi-solid fibrous asymmetric supercapacitor to obtain a self-powered full-fiber integrated sensing device, and meanwhile, winding the S-VO prepared in the step A2 on the quasi-solid fibrous asymmetric supercapacitor to obtain the S-VO x The NWs @ CNT fiber is used as a catalytic material to obtain the self-driven full-fiber integrated full-electrolysis water electronic device. The multifunctional vanadium metal organic framework-based carbon nanotube fiber, the self-driven full-fiber integrated full-electrolysis water electronic device and related intermediate products prepared in the embodiment 1 of the invention are subjected to shape and performance detection by combining the accompanying drawings of the specification:
as shown in fig. 1, fig. 1 is a multifunctional schematic diagram of a multifunctional vanadium metal organic framework-based carbon nanotube fiber and its derivatives, and fig. 1 shows that the multifunctional fiber derived from V-MOF nanowires (V-MOF nws @ cnt fiber) grown on the carbon nanotube fiber can be used for various energy storage and usage simultaneously.
As shown in fig. 2, V-MOF NW arrays having a length of about 5 μm were uniformly distributed on the surface of the CNT fibers after hydrothermal treatment.
As shown in fig. 3a, the V-MOF NWs are smooth surfaced. FIGS. 3b-d show the oxidation (V), respectively 2 O 5 Morphology of the V-MOF NWs after NWs), nitridation (VNNWs) and sulfurization (S-VOx NWs), their array structureThe retention is good. In addition, at V 2 O 5 Many nanopores appear on the surface of NWs (fig. 3 b) and VN NWs (fig. 3 c), indicating that porous structures have been formed that can increase the specific surface area to expose more reaction/absorption sites and accelerate the kinetics of ion/electron transport. For S-VO x NWs @ CNT fiber, S-VO due to partial dissolution during vulcanization reaction x The NWs size decreases.
As shown in FIG. 4, coNi-LDH NSs @ V 2 O 5 The stable potential windows of the NWs @ CNT fiber and VNNWs @ CNT fiber electrodes are 0.0 to 0.6V and-1.2 to 0.0V, respectively, so that a quasi-solid FASC having an operating voltage of 1.7V can be prepared.
As shown in fig. 5, the fiber-shaped piezoresistive sensor (FPS) exhibits a stable change in resistance signal at different pressures, which is characteristic of the piezoresistive sensor.
As seen from the polarization curve of FIG. 6a, S-VO x NWs @ CNT fiber at 10mA/cm 2 Only shows 292.5mV small OER overpotential which is better than VO x Nws @ cnt fiber; S-VO, as shown in FIG. 6b x NWs @ CNT fiber at 10mA/cm 2 HER overpotential of current density as low as 11.5mV compared to VO x The overpotential of the nws @ cnt fiber is greatly reduced.
Through the above embodiments and drawings, it is further proved that the multifunctional vanadium metal organic framework-based carbon nanotube fiber prepared by the present invention and the preparation of the self-driven full-fiber integrated full-electrolysis water electronic device effectively solve the technical problems of the present invention, and the multifunctional vanadium metal organic framework-based carbon nanotube fiber prepared by the hydrothermal method of the present invention is annealed by different processes and respectively converted into V 2 O 5 NWs @ CNT fiber, VN NWs @ CNT fiber, and S-VO x Nws @ cnt fibers (sulfur doped vanadium oxide). Using CoNi-LDH NSs @ V 2 O 5 NWs @ CNT fiber (CoNi layered double hydroxide nanosheet @ V) 2 O 5 NWs core/shell nanostructure) as the positive electrode, VN NWs @ cnt fiber as the negative electrode, assembled wound fibrous asymmetric SC (fastc) with maximum working voltage of 1.7V and high energy density;
in addition, the method can be used for producing a composite materialA fiber-like integrated device is made by twisting a fiber-like piezoresistive sensor (FPS; VNNWs @ CNT fiber also serves as a high-sensitivity piezoresistive material) together with FASC, where high-performance FASC can provide sustained output power to the FPS. Finally, S-VO x The nws @ cnt fiber electrode exhibits excellent electrocatalytic Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), and can construct a self-driven water splitting unit together with fasts. The technical problem of the invention is effectively solved, and the multifunctional material is provided, which can simultaneously meet the requirements of energy storage and utilization.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A preparation method of a multifunctional vanadium metal organic framework-based carbon nanotube fiber is characterized by comprising the following steps:
s1: adding VOSO 4 、NH 4 VO 3 Dissolving terephthalic acid in N, N-dimethylformamide, and stirring to obtain a mixed solution;
s2: transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene lining stainless steel high-pressure kettle containing nickel foam, and immersing carbon nano tube fibers;
s3: and (3) transferring the autoclave treated in the step (S2) into a drying oven for reaction, cooling to room temperature after the reaction is finished, and drying the product in vacuum overnight to obtain the V-MOF NWs @ CNT fiber, namely the multifunctional vanadium metal organic framework-based carbon nanotube fiber.
2. The method for preparing multifunctional vanadium metal organic framework-based carbon nanotube fiber according to claim 1, wherein in the step S1, the VOSO is added 4 、NH 4 VO 3 And terephthalic acid in a molar ratio of 1; the stirring temperature is 60 ℃ for a period of timeWas 8 hours.
3. The method for preparing multifunctional vanadium metal organic framework-based carbon nanotube fiber according to claim 1, wherein in the step S2, the volume of the polytetrafluoroethylene-lined stainless steel autoclave is 100mL, and the volume of the nickel foam is 4cm 2 。
4. The method for preparing the carbon nanotube fiber with the multifunctional vanadium metal organic framework according to claim 1, wherein in the step S3, the reaction temperature is 160 ℃ and the reaction time is 48 hours; and the operation of washing the product with ethanol for a plurality of times is also included between the cooling of the reaction end to room temperature and the drying under vacuum overnight, and the temperature of the drying under vacuum overnight is 40 ℃.
5. A multifunctional vanadium metal organic framework-based carbon nanotube fiber, which is prepared by the preparation method of any one of claims 1 to 4.
6. The use of the multifunctional vanadium metal organic framework-based carbon nanotube fiber according to claim 5, which comprises applying the multifunctional vanadium metal organic framework-based carbon nanotube fiber to a self-driven all-fiber integrated all-hydroelectric electronic device.
7. The use of the multifunctional vanadium metal organic framework based carbon nanotube fiber according to claim 6, wherein the use comprises the steps of:
a1: annealing the multifunctional vanadium metal organic framework-based carbon nanotube fiber in air to obtain V 2 O 5 Nws @ cnt fibers;
a2: preparing a positive electrode material: depositing CoNi-LDH nanosheets on the part of the V obtained in the step A1 by an electrochemical deposition method 2 O 5 CoNi-LDH NSs @ V on NWs @ CNT fibers 2 O 5 @ CNT fiber;
preparing a negative electrode material: adding multifunctional vanadium metal organic framework-based carbon nanotube fiber in NH 3 Performing annealing to obtain VNNWs @ CNT fibers;
preparing a catalytic material: placing the multifunctional vanadium metal organic framework-based carbon nanotube fiber and sulfur powder in a ceramic boat, placing the sulfur powder at the upstream, and annealing in argon atmosphere to obtain S-VO x Nws @ cnt fibers;
a3: preparing a quasi-solid fibrous asymmetric supercapacitor: the VNNWs @ CNT fiber and the CoNi-LDH NSs @ V prepared in the step A2 2 O 5 After the @ CNT fiber is wrapped with gel, twisting and winding to obtain the quasi-solid fibrous asymmetric supercapacitor;
preparing a fibrous piezoresistive sensor: twisting and winding four VNNWs @ CNT fibers prepared in the step A2, fixing the twisted and wound VNNWs @ CNT fibers on conductive glass by using a conductive adhesive, then uniformly covering the surface of the fixed stranded fibers with a polydimethylsiloxane prepolymer solution, and curing at 60 ℃ for 2 hours for packaging to obtain a fibrous piezoresistive sensor;
a4, preparing a self-driven full-fiber integrated full-electrolysis water electronic device:
winding the fibrous piezoresistive sensor prepared in the step A3 on the quasi-solid fibrous asymmetric supercapacitor to obtain a self-powered full-fiber integrated sensing device, and meanwhile, winding the S-VO prepared in the step A2 on the quasi-solid fibrous asymmetric supercapacitor to obtain the S-VO x The NWs @ CNT fiber is used as a catalytic material to obtain the self-driven full-fiber integrated full-electrolysis water electronic device.
8. The application of the multifunctional vanadium metal organic framework-based carbon nanotube fiber according to claim 7, wherein in the step A1, the annealing conditions are as follows: the annealing temperature is 400 ℃, the annealing time is 1 hour, and the heating rate is 5 ℃/min; in the step A2, the NH 3 The annealing conditions are as follows: the annealing temperature is 750 ℃, the annealing time is 2 hours, and the heating rate is 10 ℃/min; the annealing conditions under the argon atmosphere are as follows: heating to 300 deg.C at a heating rate of 5 deg.C/min, annealing for 1 hr, and further heatingTo 500 ℃ for a further 2 hours.
9. The use of the carbon nanotube fiber with multifunctional vanadium metal organic framework as claimed in claim 7, wherein in the step A2, the conditions of the electrochemical deposition method are as follows: at 0.05mol/L of Co (NO) 3 ) 2 ·6H 2 O and 0.05mol/L Ni (NO) 3 ) 2 ·6H 2 O was electrodeposited at room temperature as an electrolyte and measured by cyclic voltammetry for 30 cycles.
10. The application of the multifunctional vanadium metal organic framework-based carbon nanotube fiber according to claim 7, wherein in the step A3, the preparation method of the gel comprises the following steps: 1g of polyvinyl alcohol was dissolved in 10ml of 1mol/L KOH aqueous solution at 85 ℃ to prepare a polymer gel electrolyte, and magnetic stirring was carried out for 3 hours to obtain a gel.
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