CN114335427B - Three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode and preparation method and application thereof - Google Patents
Three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode, preparation method and application thereof, wherein the electrode comprises carbon nanofibers and V distributed on the carbon nanofibers 2 O 3 ；V 2 O 3 Assembling the nano sheets to form a three-dimensional sea urchin shape, and embedding the three-dimensional sea urchin shape on the surface of the carbon nano fiber in a bead-hanging shape; three-dimensional sea urchin-like VO synthesized by solvothermal method 2 And dissolving the vanadium source in a polyacrylonitrile solution to obtain a precursor solution, obtaining polymer fibers by an electrostatic spinning method from the precursor solution, and performing pre-oxidation and carbonization treatment on the polymer fibers in an inert atmosphere to obtain the composite flexible electrode. V of the invention 2 O 3 The surface of the carbon fiber is uniformly distributed in the form of beads, so that a complete conductive network is formed, the conductivity of the composite electrode is improved, and Li is reduced + The diffusion path of the material is used for relieving the volume expansion in the charge and discharge process, improving the stability of the material, and has the advantages of simple integral synthesis process, low cost and easy large-scale preparation and application.
Description
Technical Field
The invention belongs to energy storage materials, and particularly relates to a three-dimensional V2O3@carbon nanofiber composite flexible electrode, a preparation method and application thereof.
Background
In recent years, lithium ion batteries are widely applied to the fields of smart grids, high-power electric vehicles, portable electronic products and the like due to the characteristics of high energy density, high safety, environmental friendliness and the like. Graphite as Lithium Ion Batteries (LIBs)Theoretical specific capacity of anode material (372 mAh g -1 ) The requirement of the next generation lithium-based battery cannot be met due to the fact that the energy density of the lithium-ion battery is further improved, and therefore the wider application of the future energy storage technology is affected. Vanadium oxide (e.g. V 2 O 3 、VO 2 (B)、V 2 O 5 Etc.) are layered crystal compounds which are increasingly focused by people due to the characteristics of low cost, large specific capacity, abundant resources, etc., and have an open structure and various valence states (+5, +4, +3) and can realize reversible intercalation/deintercalation of lithium. Wherein, relative to other higher vanadium oxides, lower V 2 O 3 Has lower toxicity and is also receiving more attention.
But V is 2 O 3 The defects of poor conductivity, large volume change in the charge-discharge process and the like limit the rate performance and the cycle stability. In addition, the conventional electrode is easily separated from the current collector, and the metal current collector is deformed in the repeated bending process, so that the electrochemical performance of the lithium ion battery is reduced. And the conventional electrode cannot satisfy the use functions of flexibility, bending, foldability, etc., which is very disadvantageous for realizing industrialization and development of flexible lithium batteries. It is therefore particularly important to explore a flexible electrode that is simple in process, time-efficient and has high electrochemical properties.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide a high-conductivity three-dimensional V which reduces the volume expansion during the charge and discharge process 2 O 3 A carbon nanofiber composite flexible electrode; a second object of the present invention is to provide a method for producing the above-mentioned composite flexible electrode; a third object of the present invention is to provide the use of the above-described composite flexible electrode as a negative electrode material in a lithium ion battery.
The technical scheme is as follows: the invention relates to a three-dimensional V 2 O 3 The carbon nanofiber composite flexible electrode comprises carbon nanofibers and V distributed on the carbon nanofibers 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The V is 2 O 3 The three-dimensional sea urchin shape is formed by assembling the nano sheets, and the three-dimensional sea urchin shape is embedded on the surface of the carbon nano fiber in a bead-hanging shape.
Further, the V is 2 O 3 The diameter of the carbon nanofiber is 1-2 mu m, and the diameter of the carbon nanofiber is 100-300 nm.
The invention also protects the three-dimensional V 2 O 3 The preparation method of the carbon nanofiber composite flexible electrode comprises the following steps:
(1) Weighing V according to the reaction molar ratio 2 O 5 And H 2 C 2 O 4 ·2H 2 Dissolving O in deionized water, stirring until a dark blue solution is formed, then continuously adding ethanol, water and hydrogen peroxide solution for reaction, then cooling to room temperature, and obtaining VO after suction filtration, washing and drying 2 Powder;
(2) Adding polyacrylonitrile into N, N-dimethylformamide, stirring until a uniform yellow solution is formed, and adding VO 2 Adding the powder into the yellow solution prepared in the step (2), continuously stirring to obtain a precursor solution, and performing bubble removal treatment on the obtained precursor solution for later use;
(3) Carrying out electrostatic spinning on the precursor solution prepared in the step (2) to obtain V 2 O 3 A @ PAN polymer fiber;
(4) V to be prepared 2 O 3 Pre-oxidizing the @ PAN polymer fiber in an air atmosphere, carbonizing in an argon atmosphere, and cooling to room temperature to obtain three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode.
Further, in the step (2), VO 2 The mass ratio of the powder to the polyacrylonitrile is 0.3-1.5: 1. in step (2), VO 2 The powder must be added after forming a uniform yellow solution, if VO is preferred to be added to the solution 2 Then adding polyacrylonitrile, the fiber will cover V 2 O 3 No bead-hanging V can be obtained 2 O 3 Carbon nanofibers. VO (VO) 2 The specific relation exists between the powder and the polyacrylonitrile, if VO 2 If the quality is too high, the formation of interwoven carbon fibers is hindered, and the carbon fibers are broken; if the concentration of polyacrylonitrile in the spinning solution is too low, the viscosity of the spinning solution is insufficient, and beads cannot be formed on the fibers。
Further, in the step (3), the voltage applied by electrospinning is 10 to 15kV, and the flow rate is 0.5 to 0.7 mL.h -1 . In practical operation, the distance from the metal needle to the aluminum foil collector is 15cm, the relative humidity is lower than 40%, and the temperature is not higher than 30 ℃. If the humidity of the spinning environment is too high, the spinning jet is hydroscopic in the air and solidified in advance, and charges on the fiber are neutralized, so that the charge quantity of the fiber is reduced, and the phenomena of needle point filament hanging and filament floating occur.
Further, in the step (4), the pre-oxidation temperature is 230-280 ℃ and the pre-oxidation time is 2-3 h.
Further, in the step (4), the carbonization temperature is 600-700 ℃ and the carbonization time is 5-6 h.
Further, in the step (1), V 2 O 5 And H 2 C 2 O 4 ·2H 2 The reaction mole ratio of O is 1:3, a step of; the volume ratio of ethanol, water and hydrogen peroxide solution is 40:5:2; the reaction temperature is 160-200 ℃ and the reaction time is 2-4 h. Reaction molar ratio 1:3 for Forming uniform VOCs 2 O 4 The blue color of the solution was used to prepare a blue color solution,
in the step (2), the bubble removal treatment specifically means that the electrostatic spinning solution is required to be bubble removed in a vacuum dryer for 1-2 hours. If bubbles are present in the solution, this can lead to nodes or breaks in the spun fibers.
The invention further protects the three-dimensional V 2 O 3 The carbon nanofiber composite flexible electrode is applied to preparing a negative electrode material in a lithium ion battery.
The preparation principle of the invention is as follows: referring to FIG. 1, at V 2 O 5 Is a vanadium source, oxalic acid is used as a reducing agent, ethanol and water are used as solvents, and the sea urchin-shaped VO with a three-dimensional structure is synthesized by a solvothermal method 2 The method comprises the steps of carrying out a first treatment on the surface of the Then VO is carried out 2 Mixing with PAN solution to prepare electrostatic spinning solution, and preparing three-dimensional VO through electrostatic spinning 2 The @ PAN film was then pre-oxidized in air and carbonized in argon. On the one hand, VO 2 Reduction reaction is carried out to obtain V 2 O 3 ，V 2 O 3 The crystal structure of the V-shaped structure is a diamond corundum structure, wherein vanadium atoms form a three-dimensional V-V chain, and the three-dimensional V-V frame can form an open tunnel structure; on the other hand, polyacrylonitrile is converted into carbon nanofibers. Prepared three-dimensional sea urchin shape V 2 O 3 The lithium ion intercalation and deintercalation can be promoted by having large specific surface area and rich active sites; at the same time V 2 O 3 The beads are uniformly distributed on the surface of the carbon fiber in a bead-hanging shape, so that a complete conductive network is formed.
The beneficial effects are that: compared with the prior art, the invention has the remarkable advantages that: (1) The invention prepares a three-dimensional V through a simple electrostatic spinning method 2 O 3 Carbon nanofiber composite flexible electrode, V 2 O 3 The construction of the three-dimensional sea urchin structure can increase the contact area of the electrode material and the electrolyte, provide more active sites, effectively avoid the aggregation of the material in the circulation process, keep the integrity of the three-dimensional structure, improve the conductivity and the reaction kinetics of the electrode material, and improve the high-current long-time circulation performance and the rate capability of the material. (2) V of the invention 2 O 3 The surface of the carbon fiber is uniformly distributed in the form of beads, so that a complete conductive network is formed, the conductivity of the composite electrode is improved, and Li is reduced + The diffusion path of the material is used for relieving the volume expansion in the charge and discharge process and improving the stability of the material. (3) The invention synthesizes V by adopting an electrostatic spinning method 2 O 3 The carbon nanofiber composite flexible electrode is used as a lithium ion battery cathode material, so that the conductivity and the structural stability of the material can be improved, the problem of rapid capacity decay in the circulation process is solved, good flexibility and bendability are shown, and a foundation is provided for the application of a flexible lithium ion battery.
Drawings
FIG. 1 is a three-dimensional V 2 O 3 A preparation flow diagram of the carbon nanofiber composite flexible electrode;
FIG. 2 is a V produced in example 1 2 O 3 Photo drawing of carbon nanofiber composite flexible electrode;
FIG. 3 shows the process of example 1V obtained 2 O 3 SEM image of @ carbon nanofiber composite flexible electrode;
FIG. 4 is a V obtained in example 1 2 O 3 TEM image of carbon nanofiber composite flexible electrode;
FIG. 5 is V in example 6 2 O 3 Carbon nanofiber serving as anode material of lithium ion battery at 5000mAg -1 A charge-discharge cycle performance diagram at current density;
FIG. 6 is a comparative example 3 to give V 2 O 3 SEM images of (a);
fig. 7 is an SEM image of the material prepared in comparative example 5.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and examples.
Example 1
Three-dimensional V 2 O 3 The preparation method of the carbon nanofiber composite flexible electrode is shown in a figure 1, and comprises the following specific steps:
step 1) weighing V 2 O 5 And H 2 C 2 O 4 ·2H 2 O (1:3 molar ratio) was dissolved in 40mL deionized water and vigorously stirred at 70℃for 2h, until a dark blue solution formed; then, 5mL of the above solution was transferred to a 60 mL stainless steel autoclave, and 40mL of ethanol, 5mL of water and 2mL of 30% hydrogen peroxide solution were continuously added in this order and kept stirring for 1h; then solvothermal reaction is carried out for 3 hours at 180 ℃; cooling to room temperature, filtering and washing with distilled water and absolute ethyl alcohol for three times, and vacuum drying at 80 ℃ for 12 hours for later use;
step 2) weighing 0.4g of PAN, adding into 4ml of N, N-dimethylformamide, and magnetically stirring for 6 hours at 60 ℃ until a uniform yellow solution is formed;
step 3) 0.15g of VO prepared in step 1) is weighed 2 Adding the powder into the solution prepared in the step 2), continuously stirring for 24 hours to obtain a precursor solution, and removing bubbles from the obtained solution for 2 hours for later use;
step 4) carrying out electrostatic spinning on the precursor solution prepared in the step 3), wherein the applied voltage is 12kV, and the flow rate is 0.6 ml.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distance between the metal needle and the aluminum foil collector is 15cm, the relative humidity is lower than 40%, and the temperature is not higher than 30deg.C to obtain V 2 O 3 The @ PAN polymer fiber is ready for use;
step 5) V prepared in step 4 2 O 3 PAN polymer fiber at 3℃for min in an air atmosphere -1 The temperature rising rate of the catalyst is increased to the pre-oxidation temperature of 250 ℃ and the catalyst is kept for 2 hours; then in Ar atmosphere at 3 ℃ for min -1 The temperature is kept for 6 hours at the carbonization temperature of 600 ℃, and finally the three-dimensional V is obtained after cooling to the room temperature 2 O 3 Carbon nanofiber composite flexible electrode.
As shown in fig. 2, V prepared by electrospinning 2 O 3 The carbon nanofiber composite flexible film shows good flexibility and bendability.
Referring to FIG. 3, it can be seen that the prepared electrode is composed of interwoven carbon nanofibers, three-dimensional sea urchin-like V 2 O 3 Uniformly distributed on the surface of the carbon nanofiber, wherein the overall diameter is about 2 mu m, and the diameter of the carbon nanofiber is 200nm. Referring to FIG. 4, it can be seen that three-dimensional sea urchin shape V 2 O 3 Is assembled by nano-sheets, and V 2 O 3 Is embedded on the surface of the carbon nanofiber.
Example 2
Step 1) weighing V 2 O 5 And H 2 C 2 O 4 ·2H 2 O (1:3 molar ratio) was dissolved in 40mL deionized water and vigorously stirred at 70℃for 2h, until a dark blue solution formed; then, 5mL of the above solution was transferred to a 60 mL stainless steel autoclave, and 40mL of ethanol, 5mL of water and 2mL of 30% hydrogen peroxide solution were sequentially added and kept stirring for 1; then solvothermal reaction is carried out for 3 hours at 180 ℃; cooling to room temperature, filtering and washing with distilled water and absolute ethyl alcohol for three times, and vacuum drying at 80 ℃ for 12 hours for later use;
step 2) weighing 0.4g of PAN, adding into 4ml of N, N-dimethylformamide, and magnetically stirring for 6 hours at 60 ℃ until a uniform yellow solution is formed;
step 3) 0.15g of VO prepared in step 1) is weighed 2 Adding the powder into the solution prepared in the step 2), and continuously stirring for 24 hours to obtainLeading the precursor solution to pass through the bubble removing solution for 2 hours for standby;
step 4) carrying out electrostatic spinning on the precursor solution prepared in the step 3), wherein the applied voltage is 12kV, and the flow rate is 0.6 ml.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distance between the metal needle and the aluminum foil collector is 15cm, the relative humidity is lower than 40%, and the temperature is not higher than 30deg.C to obtain V 2 O 3 The @ PAN polymer fiber is ready for use;
step 5) V prepared in step 4) 2 O 3 PAN polymer fiber at 3℃for min in an air atmosphere -1 Raising the temperature rise rate to the pre-oxidation temperature of 280 ℃ and preserving the heat for 3 hours; then in Ar atmosphere at 3 ℃ for min -1 The temperature is kept for 6 hours after the carbonization temperature is raised to 700 ℃, and finally the three-dimensional V is obtained after cooling to the room temperature 2 O 3 Carbon nanofiber composite flexible electrode.
Example 3
Three-dimensional V 2 O 3 The preparation method of the carbon nanofiber composite flexible electrode comprises the following specific steps:
step 1) weighing V 2 O 5 And H 2 C 2 O 4 ·2H 2 O (1:3 molar ratio) was dissolved in 40mL deionized water and vigorously stirred at 70℃for 2h, until a dark blue solution formed; then, 5mL of the above solution was transferred to a 60 mL stainless steel autoclave, and 40mL of ethanol, 5mL of water and 2mL of 30% hydrogen peroxide solution were continuously added in this order and kept stirring for 1h; then solvothermal reaction is carried out for 3 hours at 180 ℃; cooling to room temperature, filtering and washing with distilled water and absolute ethyl alcohol for three times, and vacuum drying at 80 ℃ for 12 hours for later use;
step 2) weighing 0.4g of PAN, adding into 4mL of N, N-dimethylformamide, and magnetically stirring for 6h at 60 ℃ until a uniform yellow solution is formed;
step 3) 0.15g of VO prepared in step 1) is weighed 2 Adding the powder into the solution prepared in the step 2), continuously stirring for 24 hours to obtain a precursor solution, and removing bubbles from the obtained solution for 2 hours for later use;
step 4) carrying out electrostatic spinning on the precursor solution prepared in the step 3), wherein the applied voltage is 12kV, and the flow rate is 0.6 ml.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distance between the metal needle and the aluminum foil collector is 15cm, the relative humidity is lower than 40%, and the temperature is not higher than 30deg.C to obtain V 2 O 3 The @ PAN polymer fiber is ready for use;
step 5) V prepared in step 4 2 O 3 PAN polymer fiber at 3℃for min in an air atmosphere -1 The temperature rise rate of the catalyst is increased to the pre-oxidation temperature of 230 ℃ and the temperature is kept for 2 hours; then in Ar atmosphere at 3 ℃ for min -1 The temperature is kept for 5 hours at the carbonization temperature of 600 ℃, and finally the three-dimensional V is obtained after cooling to the room temperature 2 O 3 Carbon nanofiber composite flexible electrode.
Example 4
Three-dimensional V 2 O 3 The preparation method of the carbon nanofiber composite flexible electrode comprises the following specific steps:
step 1) weighing V 2 O 5 And H 2 C 2 O 4 ·2H 2 O (1:3 molar ratio) was dissolved in 40mL deionized water and vigorously stirred at 70℃for 2h, until a dark blue solution formed; then, 5mL of the above solution was transferred to a 60 mL stainless steel autoclave, and 40mL of ethanol, 5mL of water and 2mL of 30% hydrogen peroxide solution were continuously added in this order and kept stirring for 1h; then solvothermal reaction is carried out for 3 hours at 180 ℃; cooling to room temperature, filtering and washing with distilled water and absolute ethyl alcohol for three times, and vacuum drying at 80 ℃ for 12 hours for later use;
step 2) weighing 0.5g of PAN, adding into 4ml of N, N-dimethylformamide, and magnetically stirring for 6 hours at 60 ℃ until a uniform yellow solution is formed;
step 3) 0.15g of VO prepared in step 1) is weighed 2 Adding the powder into the solution prepared in the step 2), continuously stirring for 24 hours to obtain a precursor solution, and removing bubbles from the obtained solution for 1 hour for later use;
step 4) carrying out electrostatic spinning on the precursor solution prepared in the step 3), wherein the applied voltage is 15kV, and the flow rate is 0.7 ml.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distance between the metal needle and the aluminum foil collector is 15cm, the relative humidity is lower than 40%, and the temperature is not higher than 30deg.C to obtain V 2 O 3 The @ PAN polymer fiber is ready for use;
step 5) willV prepared in step 4 2 O 3 PAN polymer fiber at 3℃for min in an air atmosphere -1 The temperature rising rate of the catalyst is increased to the pre-oxidation temperature of 250 ℃ and the catalyst is kept for 2 hours; then in Ar atmosphere at 3 ℃ for min -1 The temperature is kept for 6 hours at the carbonization temperature of 600 ℃, and finally the three-dimensional V is obtained after cooling to the room temperature 2 O 3 Carbon nanofiber composite flexible electrode.
Example 5
Three-dimensional V 2 O 3 The preparation method of the carbon nanofiber composite flexible electrode comprises the following specific steps:
step 1) weighing V 2 O 5 And H 2 C 2 O 4 ·2H 2 O (1:3 molar ratio) was dissolved in 40mL deionized water and vigorously stirred at 70℃for 2h, until a dark blue solution formed. Then, 5mL of the above solution was transferred to a 60 mL stainless steel autoclave, and 40mL of ethanol, 5mL of water and 2mL of 30% hydrogen peroxide solution were continuously added in this order and kept stirring for 1h; then solvothermal reaction is carried out for 3 hours at 180 ℃; cooling to room temperature, filtering and washing with distilled water and absolute ethyl alcohol for three times, and vacuum drying at 80 ℃ for 12 hours for later use;
step 2) weighing 0.3g of PAN, adding into 4ml of N, N-dimethylformamide, and magnetically stirring for 6 hours at 60 ℃ until a uniform yellow solution is formed;
step 3) 0.45g of VO prepared in step 1) is weighed 2 Adding the powder into the solution prepared in the step 2, continuously stirring for 24 hours to obtain a precursor solution, and removing bubbles from the obtained solution for 2 hours for later use;
step 4) carrying out electrostatic spinning on the precursor solution prepared in the step 3, wherein the applied voltage is 10kV, and the flow rate is 0.5 ml.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distance between the metal needle and the aluminum foil collector is 15cm, the relative humidity is lower than 40%, and the temperature is not higher than 30deg.C to obtain V 2 O 3 The @ PAN polymer fiber is ready for use;
step 5) V prepared in step 4 2 O 3 PAN polymer fiber at 3℃for min in an air atmosphere -1 The temperature rising rate of the catalyst is increased to the pre-oxidation temperature of 250 ℃ and the catalyst is kept for 2 hours; then in Ar atmosphere at 3 ℃ for min -1 Is increased to 600 DEG CPreserving the carbonization temperature for 6 hours, and finally cooling to room temperature to obtain the three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode.
Comparative example 1
The specific preparation process is the same as in example 1, except that the pre-oxidation temperature in step 5) is 220 ℃ and the pre-oxidation time is 1h.
Comparative example 2
The specific preparation process is the same as in example 1, except that the carbonization temperature in step 5) is 500 ℃ and the carbonization time is 5 hours.
Comparative example 3
The specific preparation process is the same as in example 1, except that V in step 1) 2 O 5 And H 2 C 2 O 4 ·2H 2 The molar ratio of O is 1:2. referring to fig. 6, since the reaction molar ratio is less than 1:3, thus the prepared morphology is in a block shape, which indicates that a small amount of oxalic acid cannot make V 2 O 5 Complete conversion to VOCs 2 O 4 Therefore, the bead hanging structure can not be obtained by further self-assembling into a flower-like shape in hydrothermal process.
Comparative example 4
The specific preparation process is the same as in example 1, except that VO was added 2 0.2 to PAN mass ratio: 1.
comparative example 5
The specific preparation process is the same as in example 1, except that VO is added into the solution 2 Powder, and PAN is added. Referring to FIG. 7, it is apparent that the fibers are wrapped around V 2 O 3 The appearance of the hanging beads cannot be formed outside.
Characterization of the products obtained in examples 1-5 and comparative examples 1-5 is shown in Table 1 below.
Table 1 test results
As can be seen from Table 1, when V 2 O 5 And H is 2 C 2 O 4 ·H 2 O molar ratioIs 1:3, finally obtaining the three-dimensional sea urchin-shaped V 2 O 3 . When VO 2 The mass ratio of the catalyst to PAN is 0.3-1.5, the pre-oxidation temperature is 230-280 ℃, the pre-oxidation time is 2-3 h, the carbonization temperature is 600-700 ℃ and the carbonization time is 5-6h, and V with flexibility and good crystallinity can be successfully prepared 2 O 3 Carbon nanofibers.
Example 6
Three-dimensional V prepared in example 1 2 O 3 The flexible carbon nanofiber composite electrode is used as a lithium ion battery anode material, and comprises the following specific steps:
(1) Will V 2 O 3 Punching the flexible carbon nanofiber film into a circular sheet with the diameter of 12mm by using a manual punching machine, and taking the circular sheet as a working electrode;
(2) The wafer electrode with the diameter of 12mm obtained in the step (1) is used as a working electrode, a metal lithium sheet is used as a reference electrode, a Celgard wafer is used as a diaphragm, and the wafer electrode contains 1M LiPF 6 As the battery electrolyte, an organic electrolyte (EC: DEC: dmc=1:1:1); and assembling the 2032 type battery shell in a glove box filled with argon to complete the button cell, and carrying out electrochemical performance test after placing for 24 hours.
After electrochemical performance cycle test, as shown in FIG. 5, when the current density was 5000mA g -1 At the time of initial capacity of 336mAh g -1 After 8000 circles, the capacity is increased to 305mAh g -1 The capacity retention was 90%, indicating that V was produced by electrospinning 2 O 3 The flexible carbon nanofiber electrode has a stable structure and a good conductive network, improves the conductivity of the electrode and simultaneously ensures that Li + Agglomeration is not easy to occur in the transmission process, good specific capacity and excellent long-time cycling stability are provided, and the lithium ion battery electrode material has great potential.
Claims (6)
1. Three-dimensional V 2 O 3 The carbon nanofiber composite flexible electrode is characterized in that: comprising carbon nanofibers and V distributed on the carbon nanofibers 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The V is 2 O 3 The three-dimensional sea urchin shape is formed by assembling nano sheets to form a bead-hanging shapeEmbedding on the surface of the carbon nanofiber;
said three-dimensional V 2 O 3 The preparation method of the carbon nanofiber composite flexible electrode comprises the following steps:
(1) Weighing V according to the reaction molar ratio 2 O 5 And H 2 C 2 O 4 ·2H 2 Dissolving O in deionized water, stirring until a dark blue solution is formed, then continuously adding ethanol, water and hydrogen peroxide solution for reaction, then cooling to room temperature, and obtaining VO after suction filtration, washing and drying 2 Powder;
(2) Adding polyacrylonitrile into N, N-dimethylformamide, stirring until a uniform yellow solution is formed, and adding VO 2 Adding the powder into the yellow solution prepared in the step (2), continuously stirring to obtain a precursor solution, and performing bubble removal treatment on the obtained precursor solution for later use;
(3) Carrying out electrostatic spinning on the precursor solution prepared in the step (2) to obtain VO 2 A @ PAN polymer fiber;
(4) VO to be prepared 2 Pre-oxidizing the @ PAN polymer fiber in an air atmosphere, carbonizing in an argon atmosphere, and cooling to room temperature to obtain three-dimensional V 2 O 3 A carbon nanofiber composite flexible electrode;
in the step (1), V 2 O 5 And H 2 C 2 O 4 ·2H 2 The reaction mole ratio of O is 1:3, a step of; in the step (4), the pre-oxidation temperature is 230-280 ℃, the pre-oxidation time is 2-3 h, the carbonization temperature is 600-700 ℃, and the carbonization time is 5-6 h.
2. The three-dimensional V of claim 1 2 O 3 The carbon nanofiber composite flexible electrode is characterized in that: the V is 2 O 3 The diameter of the carbon nanofiber is 1-2 mu m, and the diameter of the carbon nanofiber is 100-300 nm.
3. The three-dimensional V of claim 1 2 O 3 The @ carbon nanofiber composite flexible electrode is characterized in that: in the step (2), VO 2 The mass ratio of the powder to the polyacrylonitrile is 0.3-1.5: 1.
4. the three-dimensional V of claim 1 2 O 3 The carbon nanofiber composite flexible electrode is characterized in that: in the step (3), the voltage applied by electrostatic spinning is 10-15 kV, and the flow rate is 0.5-0.7 mL.h -1 。
5. The three-dimensional V of claim 1 2 O 3 The carbon nanofiber composite flexible electrode is characterized in that: in the step (1), the volume ratio of the ethanol, the water and the hydrogen peroxide solution is 40:5:2; the reaction temperature is 160-200 ℃ and the reaction time is 2-4 h.
6. The three-dimensional V of claim 1 2 O 3 The carbon nanofiber composite flexible electrode is characterized in that: in the step (2), the bubble removal treatment specifically means that the solution is subjected to bubble removal in a vacuum dryer for 1-2 hours.
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