CN109778352B - Ti prepared by electrostatic spinning in-situ reduction4O7Nanofibers and methods thereof - Google Patents
Ti prepared by electrostatic spinning in-situ reduction4O7Nanofibers and methods thereof Download PDFInfo
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Abstract
The invention discloses Ti prepared by electrostatic spinning in-situ reduction4O7A nano fiber and a method thereof belong to the technical field of nano material preparation; ti prepared by electrostatic spinning in-situ reduction4O7The average diameter of the nano-fiber is about 100nmIs in a necklace-shaped structure, and the length of the necklace-shaped structure is more than 50 mu m; ti4O7The preparation method of the nano-fiber adopts polyvinylpyrrolidone (PVP) as a fiber template and a carbon source, and butyl titanate as a titanium source; combining an electrostatic spinning technology and a heat treatment process, and preparing a precursor PVP/butyl titanate composite nano fiber through the electrostatic spinning technology; heat treating the mixture to decompose C produced by thermal decomposition of carbon source and the titanium source to produce TiO2Under certain conditions, the Ti and the Ti are prepared by in-situ reduction of the two4O7A nanofiber; the Ti4O7The nano-fiber has the characteristics of controllable appearance, small particle size and large specific surface area; in addition, the preparation method disclosed by the invention is simple and feasible in process, strong in process controllability and easy for industrial production.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to Ti prepared by electrostatic spinning in-situ reduction4O7Nanofibers and methods thereof.
Background
Ti4O7The nanofiber material has the advantages of excellent conductivity, corrosion resistance, electrochemical stability, environmental friendliness and the like, can be used as an energy-saving, high-efficiency and environment-friendly ceramic electrode material with a great application prospect, and is expected to be applied to the field of high-performance supercapacitors. At present, Ti4O7Usually by TiO2The preparation method by the high-temperature reduction method can be divided into the following two methods according to the phase of the reducing agent: (1) solid-phase reduction method: carbon black as reducing agent and steric hindrance agent, TiO2The reduction degree of the Ti is limited by a solid phase interface, and single-phase Ti is difficult to obtain4O7The electrical conductivity of which is affected by Ti4O7Content and particle size. (2) Gas-phase reduction method: the reaction time is shortened by improving the reaction kinetics due to the good diffusivity of the reducing gas, but the Ti is severely sintered under the high-temperature reduction condition due to the lack of solid-phase carbon as a site inhibitor, so that the Ti4O7The particles are large, the specific surface area is small, and the appearance is difficult to control.
Ti obtained by the existing preparation method4O7Large particle size, small specific surface area, difficult shape control and pure Ti4O7Difficulty in phase preparation, and powdered Ti4O7When the electrode is manufactured, a 'dead volume' is easily formed due to the need of a binder and a conductive additive to block the transmission of electrons and the diffusion of electrolyte to the surface of an electrode material, so that the electrochemical performance of the electrode is reduced, and the application of the electrode in the field of high-performance supercapacitors is limited to a certain extent.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects of the prior art and provide a Ti with simple method, controllable morphology and particle size, and easy industrial production4O7An electrostatic spinning in-situ reduction preparation method of nano-fibers.
The technical scheme adopted by the invention for solving the technical problems is as follows: electrostatic spinning in-situ reduction preparation of Ti4O7A method of nanofibers, comprising the steps of:
s1: weighing butyl titanate, EtOH and HAc, and preparing a titanium source solution; weighing PVP and EtOH, preparing a polymer solution, and taking the polymer PVP as a template and a carbon source of the nanofiber;
s2: adding the titanium source solution in the S1 into the polymer solution, and uniformly stirring to prepare an electrostatic spinning solution; in the preparation process of the electrostatic spinning solution, the content of a carbon source is fixed, and the carbon/titanium ratio of the electrostatic spinning solution is regulated and controlled by adjusting the addition amount (0-1.5 g) of butyl titanate;
s3: performing electrostatic spinning on the electrostatic spinning solution prepared in the step S2 to obtain a precursor PVP/butyl titanate composite nanofiber, namely, taking polymer polyvinylpyrrolidone (PVP) as a template and a carbon source, and taking butyl titanate as a titanium source to obtain the precursor PVP/butyl titanate composite nanofiber;
s4: sintering precursor PVP/butyl titanate composite nano-fiber to obtain Ti4O7And (3) nano fibers.
Preferably, in the S1 and S2, during the preparation of the titanium source solution, the polymer solution and the electrospinning solution, magnetic stirring is adopted to uniformly mix the solutions until a light yellow clear electrospinning solution is formed.
Preferably, in the step S3, the light yellow clarified electrostatic spinning solution is filled into a needle cylinder with a stainless steel needle head, the needle cylinder is placed on a micro injection pump to be fixed, the feeding rate of the injection pump is 1-1.5 mL/h, the stainless steel needle head is connected with a high-voltage power supply, the working voltage is 8-12 kV, the stainless steel needle head is used as an aluminum foil plate for collecting precursor PVP/butyl titanate composite nanofibers and is grounded, and the working distance between the aluminum foil plate and the stainless steel needle head is kept to be 10-12 cm.
Preferably, in S4, the sintering environment of the precursor PVP/butyl titanate composite nanofiber is a vacuum atmosphere.
Preferably, in the S4, the precursor PVP/butyl titanate composite nanofiber is sintered at 1100 ℃, and in the heating sintering process, when the temperature is below 500 ℃, the heating rate is 5 ℃/min, when the temperature is above 500 ℃, the heating rate is 10 ℃/min, when the temperature is below 500 ℃, the heating rate is low, when the temperature is above 500 ℃, the heating rate is high, and the design can sufficiently remove the residual carbon content of the polymer and simultaneously keep the fiber morphology of the precursor from being damaged, thereby improving the quality of the product.
Preferably, in the step S4, the sintered precursor PVP/butyl titanate composite nanofiber is cooled to a temperature of 100 ℃ or lower and discharged to obtain Ti4O7And (3) nano fibers.
Ti prepared by adopting the method4O7Nanofibers of the formula Ti4O7The average diameter of the nano-fiber is 100nm, the nano-fiber is in a necklace-shaped structure, and the length of the nano-fiber is more than 50 mu m.
The invention has the beneficial effects that: ti of the invention4O7The electrostatic spinning in-situ reduction preparation method of the nano-fiber adopts polyvinylpyrrolidone (PVP) as a template and a carbon source, and butyl titanate (butyl titanate) as a titanium source; combining an electrostatic spinning technology and a heat treatment process, and preparing a precursor PVP/butyl titanate composite nano fiber through the electrostatic spinning technology; heat treating the mixture to decompose carbon source polymer to produce C and decompose titanium source to produce TiO2Under certain conditions, the Ti and the titanium are reduced in situ to prepare the Ti4O7And (3) nano fibers. The Ti4O7The nano-fiber has the characteristics of controllable appearance, small particle size and large specific surface area. In addition, the preparation method disclosed by the invention is simple and feasible in process, strong in process controllability and easy for industrial production.
Drawings
FIG. 1 is a view showing Ti prepared in example 3 of the present invention4O7Scanning electron microscope pictures of nanofibers;
FIG. 2 is Ti prepared in example 3 of the present invention4O7X-ray diffraction pattern of nanofibers.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely a few embodiments of the invention and are not to be taken as a comprehensive embodiment. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
Electrostatic spinning in-situ reduction preparation of Ti4O7A method of nanofibers, comprising the steps of:
s1: weighing 0g of butyl titanate, 3mL of EtOH and 3mL of HAc, stirring for 10min by adopting magnetic force, and preparing a titanium source solution after uniformly stirring; weighing 7g of PVP and 93g of EtOH, and stirring for 12 hours by adopting magnetic force to prepare a PVP/EtOH solution with the mass fraction of 7 wt%;
s2: adding the titanium source solution in the S1 into 6.43g of PVP/EtOH solution with the mass fraction of 7 wt%, and stirring for 2 hours by adopting magnetic force to prepare colorless and clear electrostatic spinning solution;
s3: the electrostatic spinning solution prepared in the S2 is filled into a needle cylinder with a stainless steel needle head and a volume of 10mL, the model of the stainless steel needle head is G21, the needle cylinder is fixed on a micro-injection pump, and the feeding rate is set to be 1 mL/h; the stainless steel needle head is connected with a high-voltage power supply, and the working voltage is 8 kV; the aluminum foil plate is used as a receiver and is grounded, and the working distance from the stainless steel needle head to the receiving plate is kept to be 12 cm; performing electrostatic spinning, collecting precursor PVP nano fiber on an aluminum foil plate, and placing the precursor PVP nano fiber in an oven at 80 ℃ for drying and storing;
s4: sintering the prepared precursor PVP nano fiber at 1100 ℃ for 2 hours under a vacuum condition, wherein in the sintering temperature rise process, the temperature rise rate is adjusted to be 5 ℃/min when the temperature is lower than 500 ℃, the temperature rise rate is adjusted to be 10 ℃/min when the temperature is higher than 500 ℃, cooling to be lower than 100 ℃ after sintering is finished, and discharging to obtain the carbon nano fiber, wherein the average diameter of the carbon nano fiber is 50nm, and the length of the carbon nano fiber is more than 50 mu m.
Example 2
Electrostatic spinning in-situ reduction preparation of Ti4O7A method of nanofibers, comprising the steps of:
s1: weighing 1g of butyl titanate, 3mL of EtOH and 3mL of HAc, stirring for 10min by adopting magnetic force, and preparing a titanium source solution after uniformly stirring; weighing 7g of PVP and 93g of EtOH, and stirring for 12 hours by adopting magnetic force to prepare a PVP/EtOH solution with the mass fraction of 7 wt%;
s2: adding the titanium source solution in the S1 into 6.43g of PVP/EtOH solution with the mass fraction of 7 wt%, and stirring for 2 hours by adopting magnetic force to prepare light yellow clear electrostatic spinning solution;
s3: the electrostatic spinning solution prepared in the S2 is filled into a needle cylinder with a stainless steel needle head and a volume of 10mL, the model of the stainless steel needle head is G21, the needle cylinder is fixed on a micro-injection pump, and the feeding rate is set to be 1.2 mL/h; the stainless steel needle head is connected with a high-voltage power supply, and the working voltage is 10 kV; the aluminum foil plate is used as a receiver and is grounded, and the working distance from the stainless steel needle to the receiving plate is kept to be 11 cm; performing electrostatic spinning, collecting precursor PVP nano fiber on an aluminum foil plate, and placing the precursor PVP nano fiber in an oven at 80 ℃ for drying and storing;
s4: sintering the prepared precursor PVP nano fiber for 2 hours at 1100 ℃ under the vacuum condition. Wherein, in the sintering temperature rise process, the temperature rise rate is adjusted to 5 ℃/min when the temperature is below 500 ℃, the temperature rise rate is adjusted to 10 ℃/min when the temperature is above 500 ℃, and the C/Ti is obtained by cooling to below 100 ℃ and discharging after sintering is finished4O7The composite nanofiber has an average fiber diameter of 80nm and a length of more than 50 μm.
Example 3
Electrostatic spinning in-situ reduction preparation of Ti4O7A method of nanofibers, comprising the steps of:
s1: weighing 1.5g of butyl titanate, 3mL of EtOH and 3mL of HAc, stirring for 10min by adopting magnetic force, and preparing a titanium source solution after uniformly stirring; weighing 7g of PVP and 93g of EtOH, and stirring for 12 hours by adopting magnetic force to prepare a PVP/EtOH solution with the mass fraction of 7 wt%;
s2: adding the titanium source solution in the S1 into 6.43g of PVP/EtOH solution with the mass fraction of 7 wt%, and stirring for 2 hours by adopting magnetic force to prepare light yellow clear electrostatic spinning solution;
s3: the electrostatic spinning solution prepared in the S2 is filled into a needle cylinder with a stainless steel needle head and a volume of 10mL, the model of the stainless steel needle head is G21, the needle cylinder is fixed on a micro-injection pump, and the feeding rate is set to be 1.5 mL/h; the stainless steel needle head is connected with a high-voltage power supply, and the working voltage is 12 kV; the aluminum foil plate is used as a receiver and is grounded, and the working distance from the stainless steel needle head to the receiving plate is kept at 10 cm; performing electrostatic spinning, collecting precursor PVP/butyl titanate composite nano-fiber on an aluminum foil plate, and placing the precursor PVP/butyl titanate composite nano-fiber in an oven at 80 ℃ for drying and storing;
s4: sintering the prepared precursor PVP/butyl titanate composite nano-fiber for 2 hours at 1100 ℃ under a vacuum condition. Wherein, in the sintering temperature rise process, when the temperature is below 500 ℃, the temperature rise rate is adjusted to 5 ℃/min, when the temperature is above 500 ℃, the temperature rise rate is adjusted to 10 ℃/min, after sintering, the temperature is cooled to below 100 ℃, and then the Ti is obtained by discharging the material out of the furnace4O7And (3) nano fibers.
For the prepared Ti4O7The results of the electron microscope scanning and the X-ray diffraction test of the nanofibers are shown in fig. 1 and 2, respectively. The Ti4O7The nano-fiber has the characteristics of controllable appearance, small particle size and large specific surface area, and the prepared Ti4O7The average diameter of the nano-fiber is 100nm, and the length is more than 50 μm.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and shall be covered by the present invention.
Claims (4)
1. Electrostatic spinning in-situ reduction preparation of Ti4O7A method of nanofibres, characterised in that the method comprises the steps of:
s1: weighing butyl titanate, EtOH and HAc, and preparing a titanium source solution; PVP and EtOH are weighed to prepare a polymer solution;
s2: adding the titanium source solution in the S1 into the polymer solution, and stirring to prepare an electrostatic spinning solution;
s3: performing electrostatic spinning on the electrostatic spinning solution prepared in the S2 to obtain a precursor PVP/butyl titanate composite nanofiber;
s4: sintering a precursor PVP/butyl titanate composite nano fiber at 1100 ℃ in a vacuum atmosphere, wherein in the process of heating and sintering, when the temperature is below 500 ℃, the heating rate is 5 ℃/min, when the temperature is above 500 ℃, the heating rate is 10 ℃/min, cooling the sintered precursor PVP/butyl titanate composite nano fiber to below 100 ℃, discharging, and thus obtaining Ti4O7And (3) nano fibers.
2. The electrospinning in-situ reduction preparation of Ti according to claim 14O7A method of nanofiber characterized by: in the S1 and S2, magnetic stirring is required to be adopted in the process of preparing the titanium source solution, the polymer solution and the electrospinning solution, so that the solutions are uniformly mixed until a pale yellow clear electrospinning solution is formed.
3. The electrospinning in-situ reduction preparation of Ti according to claim 14O7A method of nanofiber characterized by: and in the S3, filling the light yellow clear electrostatic spinning solution into a needle cylinder with a stainless steel needle, fixing the needle cylinder on a micro injection pump, wherein the feeding rate of the injection pump is 1-1.5 mL/h, the stainless steel needle is connected with a high-voltage power supply, the working voltage is 8-12 kV, the needle cylinder is grounded as an aluminum foil plate for collecting precursor PVP/butyl titanate composite nano-fibers, and the working distance between the aluminum foil plate and the stainless steel needle is kept at 10-12 cm.
4. Ti prepared by the method of claim 14O7A nanofiber characterized in that: the Ti4O7Average of nanofiberThe diameter is 100nm, the necklace-shaped structure is formed, and the length is more than 50 mu m.
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