CN112908719A - Multi-layer core-sheath structure composite filament for energy storage and preparation method thereof - Google Patents
Multi-layer core-sheath structure composite filament for energy storage and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000004146 energy storage Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 239000002071 nanotube Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000002474 experimental method Methods 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- -1 transition metal sulfide Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 6
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a multi-layer core-sheath structure composite filament for energy storage and a preparation method thereof, wherein the preparation method comprises the following steps: the titanium-based composite material comprises a titanium wire, a titanium dioxide nanotube array layer attached to the titanium wire, a porous carbon layer attached to the titanium dioxide nanotube array layer, and a compound layer attached to the porous carbon layer. According to the invention, the specific capacitance, energy density and power density of the capacitor with the core-sheath structure are further improved, and the capacitor is high in quality and low in price.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a multi-layer core-sheath structure composite filament for energy storage and a preparation method thereof.
Background
In recent years, the flexible intelligent device and the wearable electronic product keep strong growth tendency, the market is very large, and the shipment volume of wearable equipment in 2019 all the year is up to 9924 thousands of wearable equipment in the pure Chinese market according to a Chinese wearable equipment market quarterly tracking report newly issued by international data corporation IDC. The continuous and vigorous development of intelligent portable devices and wearable electronic products has promoted the development of electronic devices towards light, thin, flexible and integrated. However, the insufficient power has become a key issue for restricting the development of portable devices and wearable electronic products, and how to develop flexible ultra-high performance energy storage devices has become a key challenge. Among energy storage devices, fibrous supercapacitors have attracted considerable interest over the past decade due to their advantages of small size, arbitrary deformability, fast charge and discharge rates, and long cycle life.
The specific capacitance, energy density and power density currently used in fibrous supercapacitors are all subject to further improvement.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the multi-layer core-sheath structure composite filament for energy storage and the preparation method thereof, so that the specific capacitance, the energy density and the power density of the capacitor of the core-sheath structure are further improved, and the core-sheath structure composite filament is high in quality and low in price. To achieve the above objects and other advantages in accordance with the present invention, there is provided a multi-layered core-sheath structure composite filament for energy storage, comprising:
the titanium-based composite material comprises a titanium wire, a titanium dioxide nanotube array layer attached to the titanium wire, a porous carbon layer attached to the titanium dioxide nanotube array layer, and a compound layer attached to the porous carbon layer.
Preferably, the compound layer includes a metal oxide layer, a metal sulfide layer, and a conductive polymer layer.
A preparation method of a multi-layer core-sheath structure composite filament for energy storage comprises the following steps:
s1, respectively cleaning the titanium wires with a cleaning solution, acetone and clear water;
s2 reaction of fluorine-containing ammonium fluoride (NH)4F) Water of (2) andfixing molybdenum wire on anode in mixed solution of ethylene glycol, taking platinum as counter electrode, and carrying out anodic oxidation to form TiO2a/Ti core-sheath structure composite filament;
s3, cleaning the composite filament in the step S2 with water and ethanol respectively, and drying;
s4, drying the TiO2Placing the composite filament with the/Ti core-sheath structure in a tube furnace, and depositing on TiO by a CVD (chemical vapor deposition) method under the protection of argon2Growing a layer of carbon on the surface of the/Ti core-sheath structure composite filament to form C/TiO2a/Ti multilayer structure composite filament;
s5 in C/TiO2The surface of the/Ti multilayer structure composite wire is further modified with a layer of active material (a-M) with high pseudo capacitance to form a-M/C/TiO2a/Ti multilayer structure composite filament;
s6, respectively coating 1M sulfuric acid or phosphoric acid/PVA as solid electrolytes on the molybdenum oxide/molybdenum core-sheath structure composite wire electrodes, airing for 1-5 hours, and assembling the two electrodes in parallel to form a fibrous supercapacitor.
Preferably, the titanium wire has a diameter in the range of 20 to 3000 microns.
Preferably, the content of water in the mixed solution of water and ethylene glycol containing ammonium fluoride is 1-10V%.
Preferably, the concentration of ammonium fluoride in the mixed solution of water and ethylene glycol containing ammonium fluoride ranges from 1 to 10 wt%.
Preferably, the preparation process also comprises an anodic oxidation experiment and a CVD growth experiment, wherein the voltage range in the anodic oxidation experiment is 1-100V, the current range is 0.01-10A, and the anodic oxidation time range is 0.1-100 hours.
Preferably, in the CVD growth experiment, the gas comprises high-purity argon, hydrogen and acetylene, the temperature range is 500-800 ℃, and the experiment time range is 1-200 minutes.
Preferably, the material in step S5 includes transition metal sulfide, transition metal oxide, and conductive polymer.
Compared with the prior art, the invention has the beneficial effects that:
(1) thereby it isThe specific capacitance of the electrode material of the super capacitor taking the core-sheath structure composite filament as the electrode is more than 200mF/cm2Has wide application prospect.
(2) The problems of small specific capacitance, low energy density and power density and the like of the existing fibrous super capacitor are solved through the porous carbon layer attached to the titanium dioxide nanotube array layer and the compound layer attached to the porous carbon layer, wherein the titanium dioxide nanotube array layer attached to the titanium wire is attached to the titanium dioxide nanotube array layer.
(3) The invention also solves the problem of controllable adjustment of the performance of the fibrous energy storage electrode, and the thickness of each layer can be adjusted by adjusting the condition of anodic oxidation reaction, so that the performance of the fibrous super capacitor can be adjusted and controlled, and the energy storage electrode with controllable performance can be obtained.
(4) The invention also solves the mass production problem of the fibrous energy storage electrode, and the titanium wire reel with the diameter of more than several kilometers can be directly subjected to anodic oxidation and CVD carbon deposition.
Drawings
FIG. 1 is a schematic view of a multi-layer core-sheath composite filament for energy storage according to the present invention;
fig. 2 is SEM and TEM images of a multi-layered core-sheath structure composite filament for energy storage and a method for preparing the same according to the present invention;
FIG. 3 is a cross-sectional SEM image of a multi-layered core-sheath composite filament for energy storage and a method for preparing the same according to the present invention;
fig. 4 is an XPS spectrum of a composite filament of a multi-layered core-sheath structure for energy storage and a method for preparing the same according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described 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 of the embodiments. 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.
Referring to fig. 1-4, a multi-layered core-sheath composite filament for energy storage, comprising: the titanium wire, attach to titanium dioxide nanotube array layer on the titanium wire, attach to porous carbon layer on the titanium dioxide nanotube array layer and attach to the compound layer of porous carbon layer, porous carbon layer has higher electric double layer capacitance, and the titanium wire of core has higher electric conductive property.
Further, the compound layer includes a metal oxide layer, a metal sulfide layer, and a conductive polymer layer.
A preparation method of a multi-layer core-sheath structure composite filament for energy storage comprises the following steps:
s1, respectively cleaning the titanium wires with a cleaning solution, acetone and clear water;
s2 reaction of fluorine-containing ammonium fluoride (NH)4F) Fixing molybdenum wire on anode, using platinum as counter electrode, making anodic oxidation to form TiO2a/Ti core-sheath structure composite filament;
s3, cleaning the composite filament in the step S2 with water and ethanol respectively, and drying;
s4, drying the TiO2Placing the composite filament with the/Ti core-sheath structure in a tube furnace, and depositing on TiO by a CVD (chemical vapor deposition) method under the protection of argon2Growing a layer of carbon on the surface of the/Ti core-sheath structure composite filament to form C/TiO2a/Ti multilayer structure composite filament;
s5 in C/TiO2The surface of the/Ti multilayer structure composite wire is further modified with a layer of active material (a-M) with high pseudo capacitance to form a-M/C/TiO2a/Ti multilayer structure composite filament;
s6, respectively coating 1M sulfuric acid or phosphoric acid/PVA as solid electrolytes on the molybdenum oxide/molybdenum core-sheath structure composite wire electrodes, airing for 1-5 hours, and assembling the two electrodes in parallel to form a fibrous supercapacitor.
Further, the titanium wire has a diameter ranging from 20 micrometers to 3000 micrometers.
Further, in the mixed solution of water and ethylene glycol containing ammonium fluoride, the content of water is 1-10V%.
Further, in the mixed solution of water and ethylene glycol containing ammonium fluoride, the concentration of ammonium fluoride is in the range of 1-10 wt%.
Further, the preparation process also comprises an anodic oxidation experiment and a CVD growth experiment, wherein the voltage range in the anodic oxidation experiment is 1-100V, the current range is 0.01-10A, and the anodic oxidation time range is 0.1-100 hours.
Furthermore, in the CVD growth experiment, the gas comprises high-purity argon, hydrogen and acetylene, the temperature range is 500-800 ℃, and the experiment time range is 1-200 minutes.
Further, the material in step S5 includes transition metal sulfide, transition metal oxide, and conductive polymer.
Example 1
2ml of water and 98ml of ethylene glycol are mixed to prepare a water-ethylene glycol mixed solution with the water content of 2V percent. 0.333 g of ammonium fluoride was added to the above mixed solution to prepare a water-ethylene glycol mixed solution containing 0.3 wt% of ammonium fluoride. The solution is used as electrolyte, 1 row of titanium wires with the length of 20 cm and the diameter of 250 microns are fixed on an anode, a platinum electrode is used as the electrode, a direct current power supply is used for anodic oxidation at normal temperature, the anode is oxidized to be constant voltage of 60V for 5 hours, and the titanium oxide/titanium composite wires obtained after oxidation are taken out and dried.
The titanium oxide/titanium composite wire is placed in a tubular reaction furnace, and the temperature is raised to 650 ℃ under the protection of argon with the flow rate of 200 SCCM. After the temperature reached 650 degrees, 10SCCM of hydrogen and 20SCCM of acetylene were fed and maintained at conditions for 1 hour. The acetylene and hydrogen were then turned off, the temperature was allowed to drop to room temperature, and the composite wire (carbon/titania/titanium) after carbon deposition was removed.
Example 2
3ml of water and 97ml of ethylene glycol are mixed to prepare a water-ethylene glycol mixed solution with the water content of 3V%. 0.333 g of ammonium fluoride was added to the above mixed solution to prepare a water-ethylene glycol mixed solution containing 0.3 wt% of ammonium fluoride. The solution is used as electrolyte, 1 row of titanium wires with the length of 20 cm and the diameter of 500 microns are fixed on an anode, a platinum electrode is used as the electrode, a direct current power supply is used for anodic oxidation at normal temperature, the anode is oxidized to be constant voltage of 60V for 7 hours, and the titanium oxide/titanium composite wires obtained after oxidation are taken out and dried.
The titanium oxide/titanium composite wire is placed in a tubular reaction furnace, and the temperature is raised to 700 ℃ under the protection of argon with the flow rate of 200 SCCM. After the temperature reached 700 deg.C, 10SCCM of hydrogen and 20SCCM of acetylene were fed and maintained at conditions for 1 hour. The acetylene and hydrogen were then turned off, the temperature was allowed to drop to room temperature, and the composite wire (carbon/titania/titanium) after carbon deposition was removed.
Example 3
Preparing a molybdenum disulfide layer on the surface of the carbon/titanium oxide/titanium composite wire by a hydrothermal method to form the molybdenum disulfide/carbon/titanium oxide/titanium composite wire.
And electrodepositing and preparing a layer of manganese oxide nanowire on the surface of the carbon/titanium oxide/titanium composite wire to form the manganese oxide/carbon/titanium oxide/titanium composite wire.
The number of devices and the scale of the processes described herein are intended to simplify the description of the invention, and applications, modifications and variations of the invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (9)
1. A multi-level core-sheath structure composite filament for energy storage, comprising:
the titanium-based composite material comprises a titanium wire, a titanium dioxide nanotube array layer attached to the titanium wire, a porous carbon layer attached to the titanium dioxide nanotube array layer, and a compound layer attached to the porous carbon layer.
2. The composite filament of claim 1, wherein the compound layer comprises a metal oxide layer, a metal sulfide layer, and a conductive polymer layer.
3. The method of claim 1, wherein the method comprises the steps of:
s1, respectively cleaning the titanium wires with a cleaning solution, acetone and clear water;
s2 reaction of fluorine-containing ammonium fluoride (NH)4F) Fixing molybdenum wire on anode, using platinum as counter electrode, making anodic oxidation to form TiO2a/Ti core-sheath structure composite filament;
s3, cleaning the composite filament in the step S2 with water and ethanol respectively, and drying;
s4, drying the TiO2Placing the composite filament with the/Ti core-sheath structure in a tube furnace, and depositing on TiO by a CVD (chemical vapor deposition) method under the protection of argon2Growing a layer of carbon on the surface of the/Ti core-sheath structure composite filament to form C/TiO2a/Ti multilayer structure composite filament;
s5 in C/TiO2The surface of the/Ti multilayer structure composite wire is further modified with a layer of active material (a-M) with high pseudo capacitance to form a-M/C/TiO2a/Ti multilayer structure composite filament;
s6, respectively coating 1M sulfuric acid or phosphoric acid/PVA as solid electrolytes on the molybdenum oxide/molybdenum core-sheath structure composite wire electrodes, airing for 1-5 hours, and assembling the two electrodes in parallel to form a fibrous supercapacitor.
4. The method of claim 3, wherein the titanium wire has a diameter ranging from 20 micrometers to 3000 micrometers.
5. The method of claim 3, wherein the mixed solution of water and ethylene glycol containing ammonium fluoride has a water content of 1-10V%.
6. The method of claim 3, wherein the ammonium fluoride is present in the mixed solution of water and ethylene glycol containing ammonium fluoride in a concentration range of 1-10 wt%.
7. The method according to claim 3, wherein the process further comprises an anodic oxidation experiment and a CVD growth experiment, wherein the anodic oxidation experiment has a voltage range of 1-100V, a current range of 0.01-10A, and an anodic oxidation time range of 0.1-100 hours.
8. The method as claimed in claim 7, wherein in the CVD growth experiment, the gas comprises high purity argon, hydrogen and acetylene, the temperature is 500-1000 ℃, and the experiment time is 1-200 min.
9. The method of claim 3, wherein the property material of step S5 comprises transition metal sulfide, transition metal oxide, and conductive polymer.
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