CN114388275A - TiC nanotube array material and preparation method and application thereof - Google Patents
TiC nanotube array material and preparation method and application thereof Download PDFInfo
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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
- H01G11/24—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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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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
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Abstract
The invention discloses a TiC nanotube array material and a preparation method and application thereof. The TiC nanotube array material is formed by growing TiC nanotubes on a titanium substrate, and has high orientation and high orderliness, and the tube diameter of the TiC nanotubes is 80-150 nm. The preparation method is S1, and TiO is prepared by adopting an anodic oxidation method2A nanotube array; s2 TiO to be prepared2Heating the nanotube array to 400 ℃ at a heating rate of 5-10 ℃/min, and annealing for 2 h; s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2‑As a carbon source, electrolysis was carried out under vacuum,obtaining the TiC nanotube array material. The application is that the TiC nanotube array material is used as an electrode plate for manufacturing a super capacitor. The TiC nanotube array material prepared by the method has the advantages of large specific surface area, direct electron transfer, high energy density, good flexibility, good chemical stability and the like, and shows excellent performance of a super capacitor.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a TiC nanotube array material, a preparation method thereof and application thereof in a super capacitor.
Background
With the continuous consumption of fossil energy and the increasing environmental problems, the development of clean and renewable energy sources (wind energy, solar energy, tidal energy, etc.) has become an urgent need for social development. The supply of these energy sources is usually intermittent and seasonal due to the effects of the natural environment. Therefore, efficient energy storage and conversion technologies are very important for the utilization of renewable energy sources. The battery has higher energy density, so that the battery becomes an electronic energy storage element which is widely used, but with the continuous improvement of social requirements, the performance of the existing battery is more and more difficult to meet the requirements of production and development. How to improve the cycle life and power density of the battery and solve the problems of battery safety and environmental protection recycling is a major challenge in battery development.
At the same time of optimizing and improving the performance of the existing battery, researchers at home and abroad are continuously exploring novel energy storage elements. The super capacitor is widely concerned at home and abroad as an environment-friendly and efficient energy storage device, the energy density of the super capacitor is far higher than that of a traditional capacitor, the performances such as cycle life, power density and charge-discharge efficiency are obviously superior to those of a secondary battery, the super capacitor has the advantages of two types of energy storage devices such as the traditional capacitor and the secondary battery, and the super capacitor has great development potential. Supercapacitors, which are a typical capital-intensive industry, are at a rapidly evolving stage. Among them, a number of domestic local manufacturers such as Shanghai Oswey science and technology development Co., Ltd, Shenzhen this era new energy technology Co., Ltd, Beijing Jixing Joint Electron technology Co., Ltd should rise up, and international brands are represented by MAXWELL, Korean LSMtron, Nesscap, Japan Song, NEC-TOKIN, etc. In addition, the national and foreign famous schools, institutions and enterprises are actively developing research and development cooperation, including the modern times, the Chinese science and technology development institute, the LSMtron company, Shenzhen Wuzhou Longcar Limited company, Shenzhen research institute of the Harbin university, the Hunan university materials and engineering systems, and the like, jointly building laboratories and engineering centers, and jointly promoting the rapid development of the novel energy industry by taking the super-capacitor energy storage technology research as the core. Since the market comes, the global demand of the super capacitor is rapidly expanded, the super capacitor is widely applied to important fields and links such as national defense and military industry, rail transit, urban public transport, crane mechanical potential energy recovery, power generation, smart power grids, consumer electronics and the like, and the super capacitor becomes a novel industry with development prospects in the field of electrochemical energy storage.
However, the energy density of the super capacitor is much lower than that of the existing secondary battery, which is also a key issue facing the application and development thereof. The overall performance of the super capacitor mainly depends on electrode materials, an ideal electrode should have rich nano-structures, the transport/diffusion paths of ions and electrons can be shortened, higher kinetics can be realized, and the high specific surface area can provide more active sites for ion adsorption and redox reaction, so that the storage capacity is greatly improved. Therefore, it is very important to research and design the nanostructure electrode material.
In recent years, TiC has received attention because of its high electrical conductivity, good chemical and mechanical stability. The preparation process of TiC is mainly template method and vapor deposition method, which require high reaction temperature (>1100 ℃) and complex process. Moreover, most of the existing materials are prepared in a powder form, an additional conductive lining body and an organic adhesive are required for assembly, the increase of the conductive lining body improves the process difficulty and the cost for manufacturing the electrode, and the use of the adhesive increases the self weight of the electrode, so that the TiC energy density is reduced.
Therefore, how to prepare the high energy density TiC nanotube array material is the direction of research by those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a TiC nanotube array material, which solves the problem of low energy density in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a TiC nanotube array material is characterized in that TiC nanotubes grow on a titanium substrate and have high orientation and high orderliness, and the tube diameter of the TiC nanotubes is 80-150 nm.
Further, the TiC nanotube array material is made of TiO2The nanotube array is used as a precursor and is directly synthesized by electro-deoxidation and carbonization reaction in a low-temperature molten salt system.
Furthermore, the invention also provides a preparation method of the TiC nanotube, which solves the problems of high difficulty, high cost and the like of the preparation process in the prior art. The preparation method comprises the following steps:
s1, preparing TiO by using a system of ethylene glycol, ammonium fluoride and water as an electrolyte, a titanium sheet as a cathode and a metal sheet as an anode through an anodic oxidation method2A nanotube array; wherein, glycol is used as solvent, the proportion of ammonium fluoride added is 0.6 wt% of the glycol, and the proportion of water is 2 vol% of the glycol;
s2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 5-10 ℃/min, and annealing for 2 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1 to 0.3mol percent of CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source.
Further, the method also comprises the step of pretreating the titanium sheet before the step S1; the pretreatment specifically comprises the following steps: and (3) grinding and polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively.
Preferably, in step S1, the electrolysis voltage is 50V and the electrolysis time is 15min-1 h.
Step S3 includes:
s31, mixing molten salt CaCl2-KCl-LiCl is added into a crucible, the electrolytic furnace is sealed and is repeatedly vacuumized and flushed by high-purity argon, and after air in the furnace is completely discharged, the argon is injected into the furnace;
s32, heating the electrolytic furnace to 500-600 ℃, and pre-electrolyzing after the furnace temperature is stable;
s33, annealing TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1 to 0.3mol percent of CO is added3 2-Applying 3.3V voltage between the cathode and the anode as carbon source, and electrolyzing for 0.5 hr or more;
and S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
Preferably, the CaCl is2in-KCl-LiCl molten salt, CaCl2KCl and LiCl in a molar ratio of 4: 1: 5.
preferably, the pre-electrolysis process is as follows: and electrolyzing for 12 hours at 3V by using a graphite rod as an anode and a stainless steel rod as a cathode to remove impurities in the molten salt.
Preferably, the carbon source is directly added by adding carbonate, and the carbonate may be calcium carbonate, lithium carbonate, or the like. Or by the following means: adding 0.1mol% -0.3mol% Li into the mixed molten salt2O, and continuously introducing CO into the molten salt at 2-20 ml/min2Gas, stabilizing molten salt system for 30min-1h to form soluble CO3 2-。
Further, the application of the TiC nanotube array material to a supercapacitor is also provided. The TiC nanotube array material is used as an electrode plate for manufacturing a super capacitor; the super capacitor is composed of two electrode plates and an electrolyte clamped between the electrode plates.
Compared with the prior art, the invention has the following beneficial effects:
1. the TiC nanotube array material provided by the invention has a highly oriented and ordered array structure, provides a huge specific surface area for ion adsorption, improves diffusion channels of ions and electrolyte, and is beneficial to the rapid passing of the ions on the surface of an electrode. Meanwhile, the ordered array structure can effectively avoid the agglomeration and folding of electrode materials, greatly reduce the generation of charge storage dead zones, and compared with independent disordered nano particles, the ordered array structure can realize the loading of more active materials in unit area. The TiC nanotube array material has the advantages of large specific surface area, direct electron transfer, high energy density, good flexibility, good chemical stability and the like, shows excellent performance of a super capacitor, and has potential application value in the field of energy storage. The TiC nanotube array material is directly connected to the conductive substrate without additional adhesive or conductive additive, so that the self weight of the electrode can be reduced, the capacitor assembly is facilitated, and the flexible assembly is realized; on the other hand, a direct path is provided for the transfer of electrons from the matrix to the nanotube, and the rate capability of the material is improved.
2. The preparation method of TiC nanotube array material provided by the invention firstly adopts an anodic oxidation method to prepare metal oxide with an oriented nano structure-TiO2Performing electro-deoxidation and carbonization reaction in low-temperature molten salt by using a nanotube array to obtain a TiO2The nanotube array is used as a cathode precursor and CO is used3 2-Ions as a carbon source through TiO2Electro-deoxidation, CO3 2-The ionic electrochemical carbon precipitation and metal carbonization composite reaction successfully prepares TiO2Nanotube array (TiO)2NTAs) to TiC nanotube arrays (TiC NTAs). Compared with the high temperature condition (above 1300 ℃) of the traditional deoxidation-carbonization process, the preparation method provided by the invention can realize the preparation of the carbide under the low temperature condition of 600 ℃, and reduces the energy consumption and the cost. And the technology can be expanded to the preparation of other nano-structure metal carbides, and a feasible method is provided for the preparation of the nano-structure metal carbides.
3. The TiC nanotube array material is applied to a super capacitor, and the area specific capacitance of the super capacitor is up to 52.9 mF cm−2Has good cyclic stability and mechanical flexibility. When the current density is 0.2 mA cm−2When the energy density is up to 4.7 mu Wh cm−2Much higher than most of the electrode materials at present.
Drawings
FIG. 1 is a schematic diagram of the TiC nanotube array material of the present invention.
Fig. 2 is a scanning electron microscope image of the TiC nanotube array material prepared in example 1.
Fig. 3 is a scanning electron microscope image of the TiC nanotube array material prepared in example 2.
Fig. 4 is a scanning electron microscope image of the TiC nanotube array material prepared in example 3.
FIG. 5 is a scanning electron micrograph of the TiC nanotube array material prepared in example 4.
FIG. 6 is a scanning electron micrograph of the TiC nanotube array material prepared in comparative example 1.
FIG. 7 is a scanning electron micrograph of the TiC nanotube array material prepared in comparative example 2.
FIG. 8 is a scanning electron micrograph of the TiC nanotube array material prepared in comparative example 3.
Fig. 9 is a performance test chart of a supercapacitor, wherein: (a) 10 to 100 mV s−1CV curves at different scan rates; (b) 0.2-3 mA cm under different current densities−2A GCD curve of (1); (c) specific capacitance at different current densities; (d) energy density and power density; (e) at 3.0 mA cm−2And (3) the stability of the TiC nanotube array is cycled for 10000 times.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
TiC nanotube array material
A TiC nanotube array material is characterized in that TiC nanotubes grow on a titanium substrate and have high orientation and high orderliness, and the tube diameter of the TiC nanotubes is 80-150 nm.
Further, with TiO2The nanotube array is used as a precursor, and the TiC nanotube array is directly synthesized through electro-deoxidation and carbonization reactions in a low-temperature molten salt system.
Preparation method of TiC nanotube array material
Example 1
Referring to fig. 1, a method for preparing a TiC nanotube array material includes the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolytic voltage of 50V and the electrolytic time of 15min to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2adding-KCl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 600 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, then with annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1mol percent of CO is directly added3 2-As a carbon source, a voltage of 3.3V was applied between the cathode and the anode, and electrolysis was carried out for 0.5 h.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
This exampleThe scanning electron microscope image of the prepared TiC nanotube array material is shown in fig. 2, which shows that the tube diameter range of the TiC nanotube array material prepared in this embodiment is 80 nm-110 nm. TiO 22The nanotube array is successfully converted into a TiC nanotube array, and the nano-morphology of the TiC nanotube array is basically complete.
Example 2
A preparation method of a TiC nanotube array material comprises the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolytic voltage of 50V and the electrolytic time of 15min to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2adding-KCl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 600 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, then with annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.3mol percent of CO is directly added3 2-As a carbon source, a voltage of 3.3V was applied between the cathode and the anode, and electrolysis was carried out for 0.5 h.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
As shown in fig. 3, a scanning electron microscope image of the TiC nanotube array material prepared in this embodiment shows that the tube diameter of the TiC nanotube array material prepared in this embodiment is 80nm to 110nm, the titanium dioxide nanotube array is successfully converted into a TiC nanotube array, and the nano-morphology thereof is substantially complete.
Example 3
A preparation method of a TiC nanotube array material comprises the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolysis voltage of 50V and the electrolysis time of 1h to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2adding-KCl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 600 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, then with annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and the anode and the cathode are directly connected0.1mol% of CO is added3 2-As a carbon source, a voltage of 3.3V was applied between the cathode and the anode, and electrolysis was carried out for 0.5 h.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
As shown in fig. 4, a scanning electron microscope image of the TiC nanotube array material prepared in this embodiment shows that the tube diameter of the TiC nanotube array material prepared in this embodiment is in a range of 100nm to 150nm, the titanium dioxide nanotube array is successfully converted into a TiC nanotube array, and the nano-morphology thereof is substantially complete.
Example 4
A preparation method of a TiC nanotube array material comprises the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolysis voltage of 50V and the electrolysis time of 1h to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2adding-KCl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 600 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, then with annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1mol percent of CO is added3 2-As a carbon source. CO 23 2-The preparation method is that 0.1mol percent of Li is added into the molten salt2O, and continuously introducing CO into the molten salt at a speed of 2 ml/min2Gas, stabilize the molten salt system for 30min to obtain 0.1mol% CO3 2-. A voltage of 3.3V is applied between the cathode and the anode, and electrolysis is carried out for 1.5 h.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
As shown in fig. 5, a scanning electron microscope image of the TiC nanotube array material prepared in this embodiment shows that the tube diameter of the TiC nanotube array material prepared in this embodiment is in a range of 100nm to 150nm, the titanium dioxide nanotube array is successfully converted into a TiC nanotube array, and the nano-morphology thereof is substantially complete.
Comparative example 1
A preparation method of a TiC nanotube array material comprises the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolytic voltage of 50V and the electrolytic time of 15min to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2-KAdding Cl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 800 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, and then, annealing the TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1mol percent of CO is directly added3 2-As a carbon source, a voltage of 3.3V was applied between the cathode and the anode, and electrolysis was carried out for 0.5 h.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
As shown in fig. 6, a scanning electron microscope image of the TiC nanotube array material prepared in this embodiment shows that the structure of the nanotube in the TiC nanotube array material prepared in this embodiment is completely broken, which indicates that the morphology of the nanotube is difficult to maintain at a temperature higher than 600 ℃.
Comparative example 2
A preparation method of a TiC nanotube array material comprises the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolytic voltage of 50V and the electrolytic time of 15min to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-As a carbon source, electrolysis is carried out under vacuum to obtain sodium TiCAnd (3) a rice tube array material. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2adding-KCl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 600 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, and then, annealing the TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 1mol percent of CO is directly added3 2-As a carbon source, a voltage of 3.3V was applied between the cathode and the anode, and electrolysis was carried out for 0.5 h.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
Fig. 7 shows a scanning electron microscope image of the TiC nanotube array material prepared in this embodiment, which shows that the nanotube structure of the TiC nanotube array material prepared in this embodiment is completely broken, indicating that CO is present3 2-The nanotube morphology cannot be completely maintained at an ion concentration higher than 1 mol%.
Comparative example 3
A preparation method of a TiC nanotube array material comprises the following steps:
and S1, polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively to remove stains on the surface of the titanium sheet. Adopting an anodic oxidation method, taking a system of ethylene glycol-ammonium fluoride-water as an electrolyte, a titanium sheet as a cathode, a metal sheet as an anode, the electrolysis voltage of 50V and the electrolysis time of 1h to prepare TiO2An array of nanotubes.
S2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and annealing for 1 h;
s3, mixing molten salt CaCl2-KCl-LiCl isElectrolyte of annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source. The electrolytic process is carried out in a tubular electrolytic furnace, which comprises the following steps:
s31, mixing molten salt CaCl2adding-KCl-LiCl (40: 10:50 mol%) into a crucible, sealing the electrolytic furnace, repeatedly vacuumizing and flushing with high-purity argon, and injecting the argon into the furnace after air in the furnace is completely discharged to ensure inert atmosphere.
And S32, heating the electrolytic furnace to 600 ℃, and pre-electrolyzing after the furnace temperature is stable. In the pre-electrolysis process, a graphite rod is used as an anode, a stainless steel rod is used as a cathode, and electrolysis is carried out for 12 hours under the voltage of 3V so as to remove impurities in the molten salt.
S33, and then, annealing the TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 1mol percent of CO is directly added3 2-As a carbon source, a voltage of 3.3V was applied between the cathode and the anode, and electrolysis was carried out for 15 min.
And S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
As shown in fig. 8, a scanning electron microscope image of the TiC nanotube array material prepared in this embodiment shows that a nanotube structure of the TiC nanotube array material prepared in this embodiment is damaged, which indicates that the nanotube morphology cannot be completely maintained in an electrolysis time of less than 30 min.
Preparation and performance test of supercapacitor
Preparation of super capacitor
The TiC nanotube array material in the embodiment 2 is used as an electrode material to prepare a quasi-solid flexible solid-state supercapacitor. The super capacitor is composed of two identical TiC nanotube array electrode plates and PVA-H sandwiched between the two identical TiC nanotube array electrode plates3PO4And (3) a polymer electrolyte composition. The polyvinyl alcohol polymer functions as a separator and a solid electrolyte.
Preparation of PVA-H by solution casting method3PO4Polymer electrolyte: 2g of PVA were dissolved in 20mL of deionized water and stirred at 90 ℃ for 1h until completely dissolved. 2g of H are then added dropwise3PO4Stirring for 2h until a uniform gel is formed, and finally drying at room temperature for more than 24h to obtain the flexible solid electrolyte film.
And (II) testing the performance of the super capacitor.
And (3) carrying out performance test on the prepared super capacitor, wherein the test contents comprise: the measurement of cyclic voltammetry, constant current charge and discharge test, and cyclic lifetime test results are shown in fig. 9. In FIG. 9, (a) is 10 to 100 mV s−1CV curves at different scan rates; (b) is 0.2-3 mA cm at different current densities−2A GCD curve of (1); (c) specific capacitance under different current densities; (d) energy density and power density; (e) at 3.0 mA cm−2And (3) the stability of the TiC nanotube array is cycled for 10000 times.
As can be seen from FIG. 9, the TiC NTAs electrodes have a height of up to 52.9 mF cm−2The area ratio of the capacitor is high, and the cyclic stability and the mechanical flexibility are good. When the current density is 0.2 mA cm−2When the energy density is up to 4.7 mu Wh cm−2Much higher than most of the electrode materials at present.
Therefore, the preparation method provided by the invention can realize the preparation of the carbide under the low temperature condition of 600 ℃, and reduces the energy consumption and the cost.
The TiC nanotube array material prepared by the method has the advantages of large specific surface area, direct electron transfer, high energy density, good flexibility, good chemical stability and the like, shows excellent performance of a super capacitor, and has potential application value in the field of energy storage.
The area specific capacitance of the supercapacitor prepared by the TiC nanotube array material prepared by the method is up to 52.9 mF cm−2And has good cycling stability and mechanical flexibility. When the current density is 0.2 mA cm−2When the energy density is up to 4.7 mu Wh cm−2Much higher than most of the electrode materials at present.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (10)
1. A TiC nanotube array material is characterized in that TiC nanotubes grow on a titanium substrate, and have high orientation and high order, and the tube diameter of the TiC nanotubes is 80-150 nm.
2. The TiC nanotube array material of claim 1, wherein: the TiC nanotube array material is made of TiO2The nanotube array is used as a precursor and is directly synthesized by electro-deoxidation and carbonization reaction in a low-temperature molten salt system.
3. A preparation method of a TiC nanotube array material is characterized by comprising the following steps:
s1, preparing TiO by using a system of ethylene glycol, ammonium fluoride and water as an electrolyte, a titanium sheet as a cathode and a metal sheet as an anode through an anodic oxidation method2A nanotube array; wherein, glycol is used as solvent, the proportion of ammonium fluoride added is 0.6 wt% of the glycol, and the proportion of water is 2 vol% of the glycol;
s2 TiO to be prepared2Heating the nanotube array to 400 ℃ in a muffle furnace at a heating rate of 5-10 ℃/min, and annealing for 2 h;
s3, mixing molten salt CaCl2-KCl-LiCl as electrolyte, and annealed TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1 to 0.3mol percent of CO is added3 2-And electrolyzing under vacuum to obtain the TiC nanotube array material as a carbon source.
4. The TiC nanotube array material preparation method of claim 3, further comprising the step of pretreating the titanium sheet before step S1; the pretreatment specifically comprises the following steps: and (3) grinding and polishing the titanium sheet to a mirror surface by using sand paper, and performing ultrasonic treatment in ethanol and deionized water for 10min respectively.
5. The TiC nanotube array material preparation method of claim 3, wherein in step S1, the electrolysis voltage is 50V and the electrolysis time is 15min-1 h.
6. The TiC nanotube array material preparation method of claim 3, wherein step S3 includes:
s31, mixing molten salt CaCl2-KCl-LiCl is added into a crucible, the electrolytic furnace is sealed and is repeatedly vacuumized and flushed by high-purity argon, and after air in the furnace is completely discharged, the argon is injected into the furnace;
s32, heating the electrolytic furnace to 500-600 ℃, and pre-electrolyzing after the furnace temperature is stable;
s33, annealing TiO2The nanotube array is used as a cathode, the graphite rod is used as an anode, and 0.1 to 0.3mol percent of CO is added3 2-Applying 3.3V voltage between the cathode and the anode as carbon source, and electrolyzing for 0.5 hr or more;
and S34, cleaning the cathode product obtained after electrolysis in dilute hydrochloric acid and deionized water, and then drying in vacuum to obtain the TiC nanotube array material.
7. The TiC nanotube array material preparation method of claim 3 or 6, wherein the CaCl is2in-KCl-LiCl molten salt, CaCl2KCl and LiCl in a molar ratio of 4: 1: 5.
8. the TiC nanotube array material preparation method of claim 6, wherein the pre-electrolysis process is: and electrolyzing for 12 hours at 3V by using a graphite rod as an anode and a stainless steel rod as a cathode to remove impurities in the molten salt.
9. The TiC nanotube array material preparation method of claim 3 or 6, wherein the carbon is carbonThe source is formulated directly by adding carbonate, or by: adding 0.1mol% -0.3mol% Li into the mixed molten salt2O, and continuously introducing CO into the molten salt at 2-20 ml/min2Gas, stabilizing molten salt system for 30min-1h to form soluble CO3 2-。
The application of TiC nanotube array material, characterized in that, the TiC nanotube array material of claim 1 or 2 is used as an electrode sheet for manufacturing a super capacitor; the super capacitor is composed of two electrode plates and an electrolyte clamped between the electrode plates.
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