CN112086292A - Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method - Google Patents

Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method Download PDF

Info

Publication number
CN112086292A
CN112086292A CN201910516982.2A CN201910516982A CN112086292A CN 112086292 A CN112086292 A CN 112086292A CN 201910516982 A CN201910516982 A CN 201910516982A CN 112086292 A CN112086292 A CN 112086292A
Authority
CN
China
Prior art keywords
fiber
material layer
titanium nitride
carbon
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910516982.2A
Other languages
Chinese (zh)
Inventor
张跃钢
刘美男
刘娜
潘争辉
薛鑫
程双
周莉莎
王建飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Mengwei Power Technology Co ltd
Original Assignee
Suzhou Mengwei Power Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Mengwei Power Technology Co ltd filed Critical Suzhou Mengwei Power Technology Co ltd
Priority to CN201910516982.2A priority Critical patent/CN112086292A/en
Publication of CN112086292A publication Critical patent/CN112086292A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01G11/46—Metal oxides
    • 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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • 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
    • 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 nano-composite fiber electrode, an all-solid-state fiber super capacitor and a preparation method thereof. The nanocomposite fiber electrode includes: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a manganese oxide active material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer is composed of a plurality of titanium nitride nanowires, and the manganese oxide active material layer is composed of a plurality of manganese oxide nano sheets. The nanocomposite fiber electrode includes: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber, and a carbon material layer coating the titanium nitride nano material layer. The full-solid fibrous supercapacitor provided by the invention has the maximum working voltage of 3.5V, has the characteristics of high volume energy density and excellent flexibility, can still maintain good performance even in a bending state, and has wide application prospects in the fields of portable and wearable electronic equipment.

Description

Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method
Technical Field
The invention relates to a super capacitor, in particular to a nano composite fiber electrode, an all-solid-state fiber super capacitor, and a preparation method and application thereof, and belongs to the technical field of electrochemical energy and materials.
Background
With the rapid development of miniature portable and wearable electronic products, micro-supercapacitors (micro-SCs), particularly micro Fibrous Supercapacitors (FSCs), have drawn considerable attention due to their many advantages, such as good structural adaptability, mechanical flexibility, high power density, fast charge/discharge rates, long cycle life and significant stability. The Fibrous Super Capacitor (FSC) has the characteristics of high power density, high charging and discharging speed, long service life, high mechanical strength, high flexibility and strong knittability, and is widely applied to the field of portable and wearable electronic devicesA prospective energy storage device. However, the main problem faced by the fiber super capacitor at present is that compared with a battery, the volume energy density is relatively low, and the requirement in practical application cannot be fully met, so that the practical and industrial processes are severely limited. Therefore, the main challenge of the current fibrous supercapacitor is how to improve the volumetric energy density to a level comparable to that of a battery without sacrificing power density, cycle life and other excellent performances, and the problem to be solved by the current fibrous supercapacitor is also urgent. According to the energy density formula of the super capacitor:
Figure BDA0002095352650000011
(wherein C is capacitance, and V is operating voltage) it can be known that, in addition to capacitance, an operating voltage window is another key parameter for determining energy density, and actually, the operating voltage window of most of the current fibrous supercapacitors is about 1.0V, which greatly limits the energy density of devices. Therefore, expanding the operating voltage window of the fibrous supercapacitor is a means to effectively increase the volumetric energy density of the fibrous supercapacitor.
The method aims at the problem of bottleneck of the current fibrous supercapacitor, namely the problem of low volumetric specific energy density. In the prior art, the volumetric specific energy density of a device is improved mainly by adopting an electrode material with high specific capacity, such as a pseudocapacitance material. However, the method has a limited improvement degree on the performance of the super capacitor, and is often limited by the defects of poor conductivity of pseudo-capacitor materials and the like.
Disclosure of Invention
The invention mainly aims to provide a nano-composite fiber electrode, an all-solid-state fiber super capacitor and a preparation method thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a nanocomposite fiber electrode with a core-shell structure, which comprises: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a manganese oxide active material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer is composed of a plurality of titanium nitride nanowires, and the manganese oxide active material layer is composed of a plurality of manganese oxide nano sheets.
The embodiment of the invention provides a preparation method of a nanocomposite fiber electrode with a core-shell structure, which comprises the following steps: and sequentially growing and forming a titanium nitride nano material layer and a manganese oxide active material layer on the carbon nano tube fiber to obtain the nano composite fiber electrode.
The embodiment of the invention also provides a nanocomposite fiber electrode with a core-shell structure, which comprises: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a carbon material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer is composed of a plurality of upright titanium nitride nano wires.
The embodiment of the invention also provides a preparation method of the nanocomposite fiber electrode with the core-shell structure, which comprises the following steps: and sequentially growing and forming a titanium nitride nano material layer and a carbon material layer on the carbon nano tube fiber to obtain the nano composite fiber electrode.
The embodiment of the invention also provides an all-solid-state fiber super capacitor, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode adopts the nano composite fiber electrode with the core-shell structure, the negative electrode adopts the nano composite fiber electrode with the core-shell structure, and the electrolyte adopts an ionic liquid gel electrolyte.
The embodiment of the invention also provides a preparation method of the all-solid-state fiber super capacitor, which comprises the following steps:
soaking the anode and the cathode in the ionic liquid gel electrolyte for 10-50 min respectively; and the number of the first and second groups,
and winding the anode and the cathode, and drying and solidifying the ionic liquid gel electrolyte to obtain the all-solid-state fiber super capacitor.
Compared with the prior art, the invention has the advantages that:
1) the invention adopts the ionic liquidThe gel polymer of the body is taken as electrolyte, a high-capacity MnOx @ titanium nitride nano material with a core-shell structure is grown and prepared on the surface of a carbon nano tube fiber and taken as a positive electrode, and a C @ TiN NWs @ CNT fiber is taken as a negative electrode, so that the design and preparation of an all-solid-state Asymmetric Fiber Super Capacitor (AFSC) with the maximum working voltage of 3.5V are successfully realized, a high-volume energy density fibrous super capacitor is obtained, the record of the previously reported Fiber Super Capacitor (FSC) is broken through, and the high-volume energy density fibrous super capacitor can be even matched with some commercial planar lead-acid batteries (50-90mW h cm)-3) Comparing favorably;
2) the all-solid-state fibrous supercapacitor disclosed by the invention has the characteristics of high power density and excellent flexibility, and can still keep good performance even in a bending state. Compared with other super capacitors, the invention prepares the fiber electrode with high specific capacity, and adopts the gel electrolyte based on the ionic liquid base to obtain the flexible fibrous super capacitor with wide working window and high volume energy density.
Drawings
FIG. 1 is a schematic diagram of a process for manufacturing an all-solid-state asymmetric fiber supercapacitor according to an exemplary embodiment of the present invention.
FIG. 2a shows MnO in example 1 of the present inventionx@ TiN nanomaterial @ CNT preparation process SEM image of the original carbon nanotube fiber.
FIGS. 2b to 2c show high-magnification TiO in example 1 of the present invention2SEM image of nanomaterial @ CNT fiber electrode.
Fig. 2d is an SEM image of TiN nanomaterial @ CNT fiber electrode in example 1 of the present invention.
FIGS. 2 e-2 f are high magnification MnO in example 1 of the present inventionx@ TiN nanomaterial @ CNT fiber electrode SEM image.
FIG. 2g shows high magnification MnO in example 1 of the present inventionxAnd @ TiN nanomaterial @ CNT fiber electrode TEM image.
FIG. 2h1FIG. 2h4Are respectively the hairMnO in reference example 1xEDS elemental mapping images of Ti, N, Mn and O for @ TiN NWs core/shell nanocomposites.
FIG. 2i shows MnO in example 1 of the present inventionxHRTEM images of core shells.
FIGS. 3 a-3 f are diagrams of MnO in an exemplary embodiment of the present invention, respectivelyx@ TiN NWs @ CNT fiber electrode and MnOxResults of electrochemical performance of the @ CNT fiber electrode are shown.
FIGS. 4 a-4 e are diagrams of MnO in an exemplary embodiment of the present invention, respectivelyxThe @ TiN NWs @ CNT// C @ TiN NWs @ CNT flexible all-solid-state asymmetric fiber super capacitor has a schematic diagram of electrochemical performance results.
Fig. 5 a-5 h are schematic diagrams illustrating electrochemical performance results of the all-solid-state asymmetric fiber supercapacitor under different bending conditions according to an exemplary embodiment of the present invention.
Detailed Description
Aiming at the bottleneck problem of the current fibrous super capacitor, namely the problem of low volumetric specific energy density, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein a gel polymer containing Ionic Liquid (IL) is adopted as an electrolyte (EMIMTFSI/PVDF-HFP), MnOx @ TiN nanowires with a high-capacity core-shell structure are prepared by growing on the surface of a Carbon Nanotube (CNT) fiber and are used as a positive electrode (MnOx @ TiN nanomaterial CNT), and a C @ TiN nanomaterial @ CNT fiber is used as a negative electrode, so that the design and the preparation of an all-asymmetric solid-state fiber super capacitor (AFSC) with the maximum working voltage of 3.5V are successfully realized, and the fibrous super capacitor with high volumetric energy density is obtained. The technical solution, its implementation and principles, etc. will be further explained as follows.
Aiming at the bottleneck problem that the current fibrous super capacitor has low energy surface density, the energy and power density of the super capacitor are greatly dependent on the size of a working voltage window, so that the fibrous super capacitor with high energy density and high power density is designed and prepared by adopting a technology for widening the working voltage window and a strategy for preparing a high-specific-capacity fiber electrode. Subject to the intrinsic characteristic voltage of water (1.23V),the maximum operating voltage of the aqueous electrolyte is 1.8-2.0V, which is lower than the voltage (EDLC) (2.5V) of most commercial electric double layer capacitors. And the Ionic Liquids (ILs) are generally composed of organic cations and anions, have a wider electrochemical window, high ionic conductivity and high stability, and can improve the performance of the supercapacitor. Current phase studies show that various ionic liquids for flexible supercapacitors based on carbon materials and transition metal oxides/nitrides allow extended maximum voltages up to 3.2-3.5V while improving their maximum energy/power density. The gel polymer based on the ionic liquid is used as the electrolyte, and the working voltage of the device is widened to 3.5V. In addition, in view of the problem of limited performance of the active material due to poor conductivity, the present invention solves the problem by constructing a nanocomposite with a three-dimensional structure, i.e. by depositing the active material MnO on a nanostructure with high conductivity (TiN nanomaterial @ CNT)xThe nano-sheet method is adopted, so that the fiber electrode with high specific capacitance is obtained. Through the two strategies, the energy density, the power density and the flexibility of the original super capacitor can be obviously improved, and the preparation of the fibrous super capacitor with high volume energy density is successfully realized.
An aspect of an embodiment of the present invention provides a nanocomposite fiber electrode with a core-shell structure, including: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a manganese oxide active material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer is composed of a plurality of titanium nitride nanowires, and the manganese oxide active material layer is composed of a plurality of manganese oxide nano sheets.
In some preferred embodiments, the electrode has a three-dimensional structure.
Furthermore, the diameter of the carbon nano tube fiber is 10-50 μm.
Further, the titanium nitride nanometer material layer is composed of a plurality of upright titanium nitride nanowires (TiN NWs) grown on the surface of the carbon nanotube fiber.
Furthermore, the diameter of the titanium nitride nanowire is 100-200 nm, and the length of the titanium nitride nanowire is 0.5-2 mu m.
Further, the thickness of the titanium nitride nano material layer is 0.5-2 μm.
Further, the thickness of the manganese oxide active material layer is 50-500 nm.
Further, at least part of manganese oxide (MnO) thereinx) And nano sheets are deposited on the surface of the titanium nitride nano wire.
Another aspect of an embodiment of the present invention provides a method for preparing a nanocomposite fiber electrode with a core-shell structure, including: and sequentially growing and forming a titanium nitride nano material layer and a manganese oxide active material layer on the carbon nano tube fiber to obtain the nano composite fiber electrode.
In some preferred embodiments, the preparation method comprises:
soaking carbon nanotube fibers in a titanium source solution, carrying out hydrothermal treatment at 100-180 ℃ for 3-10 h, growing a plurality of upright titanium dioxide nanowires on the surfaces of the carbon nanotube fibers, and then carrying out thermal treatment in a reducing atmosphere to form the titanium nitride nanometer material layer.
Further, the heat treatment comprises: the heat treatment temperature is 600-800 ℃, the time is 1-3 h, and the gas for forming the reducing atmosphere comprises ammonia gas.
Further, in order to inhibit rapid hydrolysis, the titanium source solution is acidic, wherein the titanium source includes titanium n-butoxide, but is not limited thereto.
Further, the preparation method further comprises the following steps: firstly, treating the carbon nanotube fiber by oxygen plasma with the power of 100-120W for 10-30 min, and then growing the titanium dioxide nanowire on the surface of the carbon nanotube fiber.
In some preferred embodiments, the preparation method comprises: and depositing a plurality of manganese oxide nano sheets on the carbon nano tube fiber coated with the titanium nitride nano material layer by adopting an electrochemical deposition technology to form the manganese oxide active material layer.
Further, the preparation method comprises the following steps: a three-electrode system is adopted, carbon nanotube fibers coated with a titanium nitride nano material layer are used as a working electrode, and manganese oxide nano sheets are deposited on the working electrode to form the manganese oxide active material layer.
Further, the preparation method comprises the following steps: when the manganese oxide nanosheet is deposited, the adopted deposition current density is 3-8 mA cm-2The time is 30 s-5 min, and the electrolyte contains 0.01-0.1 mol/L Mn2+0.01 to 0.1mol/L of CH3COO-。
Further, the preparation method further comprises the following steps: the carbon nanotube fiber coated with the titanium nitride nano material layer is immersed into 0.1-1 mol/L of acid solution for pretreatment for 1-10 min, and then manganese oxide nano sheets are deposited on the carbon nanotube fiber coated with the titanium nitride nano material layer.
In some more specific embodiments, the preparation method of the nanocomposite fiber electrode with the core-shell structure comprises the following steps:
(1) titanium nitride (TiN) Nanowires (NWs) were prepared on CNT fibers. First, a Carbon Nanotube (CNT) fiber is treated in an oxygen plasma at 100 to 120W for 10 to 30 min. Then, 15ml of concentrated hydrochloric acid was diluted with 15ml of deionized water, and 0.5ml of titanium n-butoxide was added and mixed well. Transferring the solution into a polytetrafluoroethylene kettle (40 ml volume), immersing the pretreated CNT fiber in the solution, sealing the solution by using a stainless steel autoclave, treating the solution for 3-10 hours at the temperature of 100-180 ℃, then slowly cooling the solution to room temperature, cleaning and drying the solution to obtain TiO2NWs @ CNT fiber. Finally, the TiO obtained after the hydrothermal treatment2And (3) placing the NWs @ CNT fiber in an ammonia atmosphere, and performing heat treatment for 1-3 h at the temperature of 600-800 ℃ to obtain the titanium nitride (TiN) Nanowire (NWs) @ CNT fiber.
(2) Preparing MnOx @ TiN NWs @ CNT fibers. Firstly, the TiN NWs @ CNT fiber is immersed in 0.1-1 mol/L HCl aqueous solution for pretreatment for 1-10 min. Then, an electrochemical deposition process is carried out (solution preparation: 0.01-0.1 mol/L MnSO)4,0.01～0.1mol/L CH3COONa, 10% ethanol; electrochemical deposition parameters: the working electrode is TiN NWs @ CNT fiber; the counter electrode is a Pt electrode; the reference electrode is a saturated calomel electrode; deposition by a constant current method: the current density is 3-8 mA cm-2) MnOx nanoplates were deposited onto TiN @ CNT fibers. And finally, washing the MnOx @ TiN NWs @ CNT fiber twice by using deionized water and drying in vacuum to obtain the MnOx @ TiN NWs @ CNT fiber.
Another aspect of an embodiment of the present invention provides a nanocomposite fiber electrode with a core-shell structure, including: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a carbon material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer is composed of a plurality of upright titanium nitride nano wires.
Furthermore, the diameter of the carbon nano tube fiber is 10-50 μm.
Furthermore, the diameter of the titanium nitride nanowire is 100-200 nm, and the length of the titanium nitride nanowire is 0.5-2 mu m.
Further, the thickness of the titanium nitride nano material layer is 0.5-2 μm.
Further, the thickness of the carbon material layer is 10-50 nm.
Another aspect of the embodiments of the present invention provides a method for preparing the nanocomposite fiber electrode with the core-shell structure, including: and sequentially growing and forming a titanium nitride nano material layer and a carbon material layer on the carbon nano tube fiber to obtain the nano composite fiber electrode (namely C @ TiN NWs @ CNT fiber).
Further, the preparation method comprises the following steps: soaking the carbon nano tube fiber in a titanium source solution, carrying out hydrothermal treatment at 100-200 ℃ for 3-5 h, and growing a plurality of vertical titanium dioxide nanowires on the surface of the carbon nano tube fiber.
Further, in order to inhibit rapid hydrolysis, the titanium source solution is acidic, wherein the titanium source includes titanium n-butoxide, but is not limited thereto.
Further, the preparation method further comprises the following steps: firstly, treating the carbon nanotube fiber by oxygen plasma with the power of 100-120W for 10-30 min, and then growing the titanium dioxide nanowire on the surface of the carbon nanotube fiber.
In some preferred embodiments, the preparation method comprises: soaking the carbon nanotube fiber coated with the titanium dioxide nanowire in a 0.01-1 mol/L carbon source for 1-10 h, and then performing nitridation treatment in a reducing atmosphere to form a carbon material layer coated with a titanium nitride nanometer material layer.
Further, the temperature of the nitriding treatment is 600-1000 ℃, the time is 1-5 h, and the gas for forming the reducing atmosphere comprises ammonia gas.
Further, the carbon source includes glucose, but is not limited thereto.
In some more specific embodiments, the preparation method of the nanocomposite fiber electrode with the core-shell structure comprises the following steps:
first, a Carbon Nanotube (CNT) fiber is treated in an oxygen plasma at 100 to 120W for 10 to 30 min. Then, 15ml of concentrated hydrochloric acid was diluted with 15ml of deionized water, and 0.5ml of titanium n-butoxide was added and mixed well. Transferring the solution into a polytetrafluoroethylene kettle (40 ml volume), immersing the pretreated CNT fiber in the solution, sealing the solution by using a stainless steel autoclave, treating the solution for 3-5 hours at the temperature of 100-200 ℃, then slowly cooling the solution to room temperature, cleaning and drying the solution to obtain TiO2NWs @ CNT fiber.
Secondly, preparing C @ TiN NWs @ CNT fiber and mixing TiO2The @ CNT fiber is immersed in 0.01-1 mol/L glucose aqueous solution for 1-10 hours, and then nitrided in an ammonia atmosphere at 600-1000 ℃ for 1-5 hours.
The invention further provides an all-solid-state fiber supercapacitor, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode adopts the core-shell structure nano composite fiber electrode, the negative electrode adopts the core-shell structure nano composite fiber electrode, and the electrolyte adopts an ionic liquid gel electrolyte.
Further, the ionic liquid gel electrolyte is formed by drying the gel electrolyte.
Further, the gel electrolyte comprises an ionic liquid, a polymer and a solvent.
Still further, the ionic liquid comprises EMIMTFSI, the polymer comprises PVDF-HFP, and the solvent comprises acetone, but is not limited thereto.
Furthermore, the mass ratio of the ionic liquid to the polymer is (1-10): (1-15).
Further, an ionic liquid gel electrolyte (EMIMTFSI/PVDF-HFP) was prepared: mixing 1-10 g of EMIMTFSI and 1-15 g of PVDF-HFP in 10-50 mL of acetone, and then magnetically stirring the mixture for 0.5-3 h until the polymer particles are completely dissolved and the solution becomes uniform. After the acetone is evaporated, the solution forms a solvent-free gel electrolyte.
In another aspect of the embodiments of the present invention, there is provided a method for preparing the foregoing all-solid-state fiber supercapacitor, including:
soaking the anode and the cathode in the ionic liquid gel electrolyte for 10-50 min respectively; and the number of the first and second groups,
and winding the anode and the cathode, and drying and solidifying the ionic liquid gel electrolyte to obtain the all-solid-state fiber super capacitor.
Further, the preparation method comprises the following steps:
assembling the MnOx @ TiN NWs @ CNT// C @ TiN NWs @ CNT flexible all-solid-state asymmetric fiber super capacitor, and testing the electrochemical performance of the super capacitor. Firstly, soaking MnOx @ TiN NWs @ CNT fibers and C @ TiN NWs @ CNT fibers in an ionic liquid gel electrolyte for 10-50 min and then drying. And finally, winding the two fiber electrodes together and drying the two fiber electrodes overnight until the ionic liquid gel electrolyte is completely solidified, thus obtaining the successfully assembled all-solid-state asymmetric fiber supercapacitor. Electrochemical performance testing of the devices was performed in an argon-filled glove box with <1ppm moisture.
In conclusion, the invention adopts the gel polymer containing the ionic liquid as the electrolyte, prepares the MnOx @ titanium nitride nano material with the high-capacity core-shell structure as the anode by growing on the surface of the carbon nano tube fiber, and successfully realizes the design and preparation of the all-solid-state Asymmetric Fiber Super Capacitor (AFSC) with the maximum working voltage of 3.5V by taking the C @ TiN NWs @ CNT fiber as the cathode, thereby obtaining the fibrous super capacitor with high volume energy density. The all-solid-state fibrous supercapacitor disclosed by the invention has the characteristics of high power density and excellent flexibility, and can still keep good performance even in a bending state. Compared with other super capacitors, the invention prepares the fiber electrode with high specific capacity, and adopts the gel electrolyte based on the ionic liquid base to obtain the flexible fibrous super capacitor with wide working window and high volume energy density.
The technical solutions in the embodiments of the present invention will be described in detail below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Referring to fig. 1, the preparation steps of the all-solid Asymmetric Fiber Supercapacitor (AFSC) in the present embodiment are as follows:
preparing titanium nitride (TiN) Nanowires (NW) on CNT fibers. First, Carbon Nanotube (CNT) fibers were treated in an oxygen plasma at 100W for 15 min. Then, 15ml of concentrated hydrochloric acid was diluted with 15ml of deionized water, and 0.5ml of titanium n-butoxide was added and mixed well. The solution was transferred to a teflon kettle (40 ml volume), the pretreated CNT fiber was immersed therein, sealed with a stainless steel autoclave, treated at 150 ℃ for 5 hours, then slowly cooled to room temperature, washed and dried to obtain TiO2NWs @ CNT fiber. Finally, the TiO obtained after the hydrothermal treatment2And (3) putting the NWs @ CNT fiber in an ammonia atmosphere, and carrying out heat treatment for 3h at the temperature of 600 ℃ to obtain the TiN NWs @ CNT fiber.
② preparing MnOx @ TiN NWs @ CNT fibers. First, TiN NWs @ CNT fibers were pre-treated by immersing them in 0.5mol/L HCl aqueous solution for 3 min. Then, an electrochemical deposition process is carried out (solution preparation: 0.05mol/L MnSO)4,0.05mol/L CH3COONa, 10% ethanol; electrochemical deposition of ginsengNumber: the working electrode is TiN NWs @ CNT fiber; the counter electrode is a Pt electrode; the reference electrode is a saturated calomel electrode; deposition by a constant current method: the current density was 5mA cm-2Deposition time 2min) MnOx nanoplates were deposited onto TiN @ CNT fibers. And finally, washing the MnOx @ TiN NWs @ CNT fiber twice by using deionized water and drying in vacuum to obtain the MnOx @ TiN NWs @ CNT fiber.
Preparing C @ TiN NWs @ CNT fiber and preparing TiO2@ CNT fibers were soaked in 0.05mol/L aqueous glucose solution for 5h, and then nitrided at 800 ℃ for 3h in an ammonia atmosphere.
Preparing an ionic liquid gel electrolyte (EMIMTFSI/PVDF-HFP): 10g of EMIMTFSI and 15g of PVDF were mixed in 20mL of acetone, and the mixture was then magnetically stirred for 2h until the polymer particles were completely dissolved and the solution became homogeneous. After the acetone is evaporated, the solution forms a solvent-free gel electrolyte.
Assembling the MnOx @ TiN NWs @ CNT// C @ TiN NWs @ CNT flexible all-solid-state asymmetric fiber super capacitor, and testing the electrochemical performance of the super capacitor. Firstly, MnOx @ TiN NWs @ CNT fibers and C @ TiN NWs @ CNT fibers are soaked in an ionic liquid gel electrolyte for 30min and then dried. And finally, winding the two fiber electrodes together and drying the two fiber electrodes overnight until the ionic liquid gel electrolyte is completely solidified, thus obtaining the successfully assembled all-solid-state asymmetric fiber supercapacitor. Electrochemical performance testing of the devices was performed in an argon-filled glove box with <1ppm moisture.
FIGS. 2 a-2 i are MnOxThe morphological structure characterization of each substance in the preparation process of @ TiN NWs @ CNT. Wherein, FIG. 2a is an SEM image of the initial carbon nanotube fiber; FIG. 2 b-FIG. 2c are high power TiO2SEM images of NWs @ CNT fiber electrodes; FIG. 2d is an SEM image of a TiN NWs @ CNT fiber electrode; FIG. 2 e-FIG. 2f are high magnification MnOxSEM images of @ TiN NWs @ CNT fiber electrode; fig. 2g is a TEM image thereof. FIG. 2h1FIG. 2h4Respectively being MnOxEDS element mapping images of Ti, N, Mn and O of the @ TiN NWs core/shell nanocomposite; FIG. 2i is MnOxHRTEM images of the nucleocapsids, taken from the red circled portion of fig. 2 g.
Example 2
Preparing titanium nitride (TiN) Nanowires (NW) on CNT fibers. First, a Carbon Nanotube (CNT) fiber was treated in an oxygen plasma at 120W for 10 min. Then, 15ml of concentrated hydrochloric acid was diluted with 15ml of deionized water, and 0.5ml of titanium n-butoxide was added and mixed well. Transferring the solution into a polytetrafluoroethylene kettle (40 ml volume), immersing the pretreated CNT fiber therein, sealing with a stainless steel autoclave, treating at 100 deg.C for 10 hr, slowly cooling to room temperature, washing, and drying to obtain TiO2NWs @ CNT fiber. Finally, the TiO obtained after the hydrothermal treatment2And (3) putting the NWs @ CNT fiber in an ammonia atmosphere, and carrying out heat treatment for 2h at 700 ℃ to obtain the titanium nitride TiN NWs @ CNT fiber.
② preparing MnOx @ TiN NWs @ CNT fibers. First, TiN NWs @ CNT fibers were pre-treated by immersing them in 0.1mol/L HCl aqueous solution for 10 min. Then, an electrochemical deposition process is carried out (solution preparation: 0.01mol/L MnSO)4,0.01mol/L CH3COONa, 10% ethanol; electrochemical deposition parameters: the working electrode is TiN NWs @ CNT fiber; the counter electrode is a Pt electrode; the reference electrode is a saturated calomel electrode; deposition by a constant current method: the current density was 3mA cm-2Deposition time 5min) MnOx nanoplates were deposited onto TiN @ CNT fibers. And finally, washing the MnOx @ TiN NWs @ CNT fiber twice by using deionized water and drying in vacuum to obtain the MnOx @ TiN NWs @ CNT fiber.
Preparing C @ TiN NWs @ CNT fiber and preparing TiO2@ CNT fibers were soaked in 0.01mol/L aqueous glucose solution for 10h, and then nitrided at 600 ℃ for 5h in an ammonia atmosphere.
Example 3
Preparing titanium nitride (TiN) Nanowires (NW) on CNT fibers. First, Carbon Nanotube (CNT) fibers were treated in an oxygen plasma at 110W for 30 min. Then, 15ml of concentrated hydrochloric acid was diluted with 15ml of deionized water, and 0.5ml of titanium n-butoxide was added and mixed well. Transferring the solution to a polytetrafluoroethylene kettle (40 ml volume), immersing the pretreated CNT fiber therein, sealing with a stainless steel autoclave, treating at 180 deg.C for 3 hr, slowly cooling to room temperature, washing, and drying to obtain TiO2NWs @ CNT fiber. Finally, heating the waterTiO obtained after treatment2And (3) putting the NWs @ CNT fiber in an ammonia atmosphere, and carrying out heat treatment for 1h at the temperature of 800 ℃ to obtain the TiN NWs @ CNT fiber.
② preparing MnOx @ TiN NWs @ CNT fibers. First, TiN NWs @ CNT fibers were pre-treated by immersing them in 1mol/L HCl aqueous solution for 1 min. Then, an electrochemical deposition process is carried out (solution preparation: 0.1mol/L MnSO)4,0.1mol/L CH3COONa, 10% ethanol; electrochemical deposition parameters: the working electrode is TiN NWs @ CNT fiber; the counter electrode is a Pt electrode; the reference electrode is a saturated calomel electrode; deposition by a constant current method: the current density was 8mA cm-2Deposition time 30s) MnOx nanoplates were deposited onto TiN @ CNT fibers. And finally, washing the MnOx @ TiN NWs @ CNT fiber twice by using deionized water and drying in vacuum to obtain the MnOx @ TiN NWs @ CNT fiber.
Preparing C @ TiN NWs @ CNT fiber and preparing TiO2@ CNT fibers were immersed in 1mol/L aqueous glucose solution for 1h, and then nitrided under an ammonia atmosphere at 1000 ℃ for 1 h.
The electrochemical performance of the electrode and the device of the all-solid-state Asymmetric Fiber Super Capacitor (AFSC) is characterized in that:
FIGS. 3 a-3 f are diagrams of MnO in an exemplary embodiment of the present invention, respectivelyx@ TiN NWs @ CNT fiber electrode and MnOxResults of electrochemical performance of the @ CNT fiber electrode are shown.
FIGS. 4 a-4 e are diagrams of MnO in an exemplary embodiment of the present invention, respectivelyxThe @ TiN NWs @ CNT// C @ TiN NWs @ CNT flexible all-solid-state asymmetric fiber super capacitor has a schematic diagram of electrochemical performance results.
Fig. 5 a-5 h are schematic diagrams illustrating electrochemical performance results of the all-solid-state asymmetric fiber supercapacitor under different bending conditions according to an exemplary embodiment of the present invention.
The above test results show that the present invention successfully obtains AFSC (MnO) having a maximum operating voltage of 3.5V by using gel polymer containing Ionic Liquid (IL) as electrolyte (EMIMTFSI/PVDF-HFP)x@ TiN NWs @ CNT// C @ TiN NWs @ CNT). The optimized AFSC can reach 61.2mW h cm-3The ultra-high volume energy density of (2) breaks the record of the Fiber Super Capacitor (FSC) reported before, evenTo a certain commercial plane lead-acid battery (50-90mW h cm)-3). The all-solid-state fiber super capacitor also has a thickness of 10.1W cm-3And can still have 92.7% capacity retention after 1000 cycles under 90-degree bending, and shows excellent flexibility.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A nanocomposite fiber electrode of a core-shell structure, characterized by comprising: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a manganese oxide active material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer is composed of a plurality of titanium nitride nanowires, and the manganese oxide active material layer is composed of a plurality of manganese oxide nano sheets.
2. The core-shell structured nanocomposite fiber electrode according to claim 1, characterized in that: the electrode has a three-dimensional structure; and/or the diameter of the carbon nano tube fiber is 10-50 μm; and/or the titanium nitride nanometer material layer consists of a plurality of upright titanium nitride nanowires growing on the surface of the carbon nanotube fiber; preferably, the diameter of the titanium nitride nanowire is 100-200 nm, and the length of the titanium nitride nanowire is 0.5-2 μm; and/or the thickness of the titanium nitride nano material layer is 0.5-2 μm; and/or the thickness of the manganese oxide active material layer is 50-500 nm; and/or, wherein at least part of the manganese oxide nano-sheets are deposited on the surface of the titanium nitride nano-wires.
3. The method for preparing a nanocomposite fiber electrode of a core-shell structure according to claim 1 or 2, characterized by comprising: and sequentially growing and forming a titanium nitride nano material layer and a manganese oxide active material layer on the carbon nano tube fiber to obtain the nano composite fiber electrode.
4. The production method according to claim 3, characterized by comprising:
soaking carbon nanotube fibers in a titanium source solution, carrying out hydrothermal treatment at 100-180 ℃ for 3-10 h, growing a plurality of upright titanium dioxide nanowires on the surfaces of the carbon nanotube fibers, and then carrying out heat treatment in a reducing atmosphere to form the titanium nitride nano material layer;
preferably, the heat treatment comprises: the adopted heat treatment temperature is 600-800 ℃, the time is 1-3 h, and the gas for forming the reducing atmosphere comprises ammonia gas;
preferably, the titanium source solution is acidic, wherein the titanium source comprises titanium n-butoxide;
preferably, the preparation method further comprises: firstly, treating the carbon nanotube fiber by oxygen plasma with the power of 100-120W for 10-30 min, and then growing the titanium dioxide nanowire on the surface of the carbon nanotube fiber.
5. The production method according to claim 3, characterized by comprising: depositing a plurality of manganese oxide nano sheets on the carbon nano tube fiber coated with the titanium nitride nano material layer by adopting an electrochemical deposition technology to form a manganese oxide active material layer;
preferably, the preparation method comprises the following steps: adopting a three-electrode system, taking carbon nanotube fiber coated with a titanium nitride nano material layer as a working electrode, and depositing manganese oxide nano sheets on the working electrode to form the manganese oxide active material layer;
particularly preferably, the preparation method comprises the following steps: when the manganese oxide nanosheet is deposited, the adopted deposition current density is 3-8 mA cm-2The time is 30 s-5 min, and the electrolyte contains 0.01-0.1 mol/L Mn2+0.01 to 0.1mol/L of CH3COO-；
Preferably, the preparation method further comprises: the carbon nanotube fiber coated with the titanium nitride nano material layer is immersed into 0.1-1 mol/L of acid solution for pretreatment for 1-10 min, and then manganese oxide nano sheets are deposited on the carbon nanotube fiber coated with the titanium nitride nano material layer.
6. A nanocomposite fiber electrode of a core-shell structure, characterized by comprising: the carbon nano tube fiber comprises a carbon nano tube fiber, a titanium nitride nano material layer coating the carbon nano tube fiber and a carbon material layer coating the titanium nitride nano material layer; wherein the titanium nitride nano material layer consists of a plurality of upright titanium nitride nanowires;
preferably, the diameter of the carbon nanotube fiber is 10-50 μm; and/or the diameter of the titanium nitride nanowire is 100-200 nm, and the length of the titanium nitride nanowire is 0.5-2 mu m; and/or the thickness of the titanium nitride nano material layer is 0.5-2 μm; and/or the thickness of the carbon material layer is 10-50 nm.
7. The method for preparing a nanocomposite fiber electrode with a core-shell structure according to claim 6, comprising: and sequentially growing and forming a titanium nitride nano material layer and a carbon material layer on the carbon nano tube fiber to obtain the nano composite fiber electrode.
8. The production method according to claim 7, characterized by comprising:
soaking carbon nanotube fibers in a titanium source solution, carrying out hydrothermal treatment at 100-200 ℃ for 3-5 h, and growing a plurality of upright titanium dioxide nanowires on the surfaces of the carbon nanotube fibers;
preferably, the titanium source solution is acidic, wherein the titanium source comprises titanium n-butoxide;
preferably, the preparation method further comprises: treating the carbon nanotube fiber for 10-30 min by oxygen plasma with the power of 100-120W, and then growing the titanium dioxide nanowire on the surface of the carbon nanotube fiber;
preferably, the preparation method comprises the following steps: soaking the carbon nanotube fiber coated with the titanium dioxide nanowire in 0.01-1 mol/L carbon source for 1-10 h, and then performing nitridation treatment in a reducing atmosphere to form a carbon material layer coated with a titanium nitride nanometer material layer; particularly preferably, the temperature of the nitriding treatment is 600-1000 ℃, the time is 1-5 h, and the gas for forming the reducing atmosphere comprises ammonia gas; particularly preferably, the carbon source comprises glucose.
9. An all-solid-state fiber super capacitor comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the anode adopts the nano composite fiber electrode with the core-shell structure as claimed in claim 1 or 2, the cathode adopts the nano composite fiber electrode with the core-shell structure as claimed in claim 6, and the electrolyte adopts ionic liquid gel electrolyte; preferably, the ionic liquid gel electrolyte is formed by drying a gel electrolyte; preferably, the gel electrolyte comprises an ionic liquid, a polymer and a solvent; particularly preferably, the ionic liquid comprises EMIMTFSI, the polymer comprises PVDF-HFP, and the solvent comprises acetone; particularly preferably, the mass ratio of the ionic liquid to the polymer is (1-10): (1-15).
10. The method for preparing the all-solid-state fiber supercapacitor according to claim 9, comprising:
soaking the anode and the cathode in the ionic liquid gel electrolyte for 10-50 min respectively; and the number of the first and second groups,
and winding the anode and the cathode, and drying and solidifying the ionic liquid gel electrolyte to obtain the all-solid-state fiber super capacitor.
CN201910516982.2A 2019-06-14 2019-06-14 Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method Pending CN112086292A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910516982.2A CN112086292A (en) 2019-06-14 2019-06-14 Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910516982.2A CN112086292A (en) 2019-06-14 2019-06-14 Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method

Publications (1)

Publication Number Publication Date
CN112086292A true CN112086292A (en) 2020-12-15

Family

ID=73734066

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910516982.2A Pending CN112086292A (en) 2019-06-14 2019-06-14 Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method

Country Status (1)

Country Link
CN (1) CN112086292A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115410835A (en) * 2022-08-29 2022-11-29 西北工业大学宁波研究院 Multifunctional vanadium metal organic framework-based carbon nanotube fiber and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104240967A (en) * 2014-09-26 2014-12-24 东南大学 Polyaniline-manganese dioxide-titanium nitride nanowire array composite material and preparation method and application thereof
CN104465130A (en) * 2014-12-16 2015-03-25 吉林大学 Method for preparing super capacitor electrode material
CN104616905A (en) * 2015-01-09 2015-05-13 东南大学 Polyaniline-carbon layer-titanium nitride nanowire array composite material and preparation method and application thereof
CN106449128A (en) * 2016-09-28 2017-02-22 东南大学 Integrated heteropolyacid-modified polyaniline/titanium nitride core-shell nanowire array composite material and preparation method and application thereof
CN107978463A (en) * 2017-12-08 2018-05-01 天津工业大学 A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide
US20180261401A1 (en) * 2015-09-16 2018-09-13 B/E Aerospace Systems Gmbh Composite comprising cnt fibres and an ionic conducting compound as part of an energy storage device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104240967A (en) * 2014-09-26 2014-12-24 东南大学 Polyaniline-manganese dioxide-titanium nitride nanowire array composite material and preparation method and application thereof
CN104465130A (en) * 2014-12-16 2015-03-25 吉林大学 Method for preparing super capacitor electrode material
CN104616905A (en) * 2015-01-09 2015-05-13 东南大学 Polyaniline-carbon layer-titanium nitride nanowire array composite material and preparation method and application thereof
US20180261401A1 (en) * 2015-09-16 2018-09-13 B/E Aerospace Systems Gmbh Composite comprising cnt fibres and an ionic conducting compound as part of an energy storage device
CN106449128A (en) * 2016-09-28 2017-02-22 东南大学 Integrated heteropolyacid-modified polyaniline/titanium nitride core-shell nanowire array composite material and preparation method and application thereof
CN107978463A (en) * 2017-12-08 2018-05-01 天津工业大学 A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KAIBING XU: "Hierarchical assembly of manganese dioxide nanosheets on one-dimensional titanium nitride nanofibers for high-performance supercapacitors", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 *
XIHONG LU: "Improving the cycling stability of metal-nitride supercapacitor electrodes with a thin carbon shell", 《ADVANCED ENERGY MATERIALS》 *
ZHENGHUI PAN: "All‐Solid‐State Fiber Supercapacitors with Ultrahigh Volumetric Energy Density and Outstanding Flexibility", 《ADVANCED ENERGY MATERIALS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115410835A (en) * 2022-08-29 2022-11-29 西北工业大学宁波研究院 Multifunctional vanadium metal organic framework-based carbon nanotube fiber and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN102683710B (en) Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof
CN105047423B (en) A kind of flexibility symmetric form fake capacitance ultracapacitor and preparation method thereof
CN104616910B (en) Carbon coating titanium-based nano array material and its preparation method and application
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
TW201840042A (en) Anode of lithium-ion battery and flexible lithium-ion battery using the same
CN109616331B (en) Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof
CN106848251A (en) A kind of preparation method of CNT lithium titanate composite anode material
CN108946798B (en) Linear hierarchical structure lithium titanate material and preparation and application thereof
CN110335758B (en) Cobalt manganate-nitrogen-doped hollow carbon sphere composite material with core-shell structure and preparation method and application thereof
CN106410153A (en) Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof
CN108630449B (en) Flexible asymmetric super capacitor with ultrahigh energy density and preparation method thereof
CN107204450A (en) The preparation method and applications of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs)
CN107317011A (en) A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping
Zhang et al. Review of Design Routines of MXene Materials for Magnesium‐Ion Energy Storage Device
CN107045948A (en) NaxMnO2Positive electrode, preparation method and applications
CN106848282B (en) Negative electrode material for non-aqueous electrolyte secondary battery and preparation method and application thereof
CN104733189B (en) Lithium ion-type supercapacitor ternary composite negative electrode material and preparation method thereof
KR20130047885A (en) Method for fabrication of charge storage in multi-walled carbon nanotube-niooh nano composites
CN109326453A (en) A kind of polypyrrole composite electrode material for super capacitor and preparation method thereof based on electrostatic spinning nano fiber resultant yarn technology
CN112086292A (en) Nano-composite fiber electrode, all-solid-state fiber super capacitor and preparation method
CN108878160B (en) Foamed nickel/ITO-NWs material, supercapacitor and preparation method of supercapacitor
CN110957145A (en) Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof
Zhou et al. Evaporation induced uniform polypyrrole coating on CuO arrays for free-standing high lithium storage anode
CN109449008A (en) A kind of preparation method of the hollow core-shell structure electrode material of self-supporting and its application in lithium-sulfur cell and supercapacitor
CN110098066B (en) Nano composite fiber electrode with core-shell structure and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20201215