CN111584839B - Porphyrin compound doped vanadium pentoxide sol composite material and preparation method and application thereof - Google Patents

Porphyrin compound doped vanadium pentoxide sol composite material and preparation method and application thereof Download PDF

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CN111584839B
CN111584839B CN202010376441.7A CN202010376441A CN111584839B CN 111584839 B CN111584839 B CN 111584839B CN 202010376441 A CN202010376441 A CN 202010376441A CN 111584839 B CN111584839 B CN 111584839B
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vanadium pentoxide
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pentoxide sol
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porphyrin compound
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CN111584839A (en
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吴黎明
储昭龙
安琴友
麦立强
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Wuhan University of Technology WUT
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Abstract

The invention relates to a porphyrin compound doped vanadium pentoxide sol composite material and a preparation method thereof, and the material can be used as a potential application material of a sodium ion battery anode material with long service life and excellent cycling stability. From TPyP-V of different lengths2O5·nH2The O nanowires are assembled, the width of each nanowire is 80-100 nanometers, and the length of each nanowire is 10-50 micrometers. The invention has the beneficial effects that: the nano-wire composite material of the porphyrin compound doped with the vanadium pentoxide sol can be used as a potential application material of a long-life, excellent cycle stability and high-magnification sodium ion battery anode material.

Description

Porphyrin compound doped vanadium pentoxide sol composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of new energy materials and devices, and particularly relates to a porphyrin compound doped vanadium pentoxide sol composite material and a preparation method thereof.
Background
In recent years, along with the popularization and application of lithium ion batteries, the shortage of lithium metal resources and the increase of price enable people to find a novel battery system, and because sodium has the property similar to that of lithium and has wider resource distribution, people put eyes on the sodium ion batteries. Since the relative atomic mass of sodium is more than 3 times that of lithium, but the standard potential of sodium (2.71V) is higher than that of lithium (-3.04V), the energy density of a lithium ion battery may not be theoretically achieved by a sodium ion battery. However, sodium ion batteries may have broader applications than lithium batteries, with the support of high voltage grids, compared to the cost and life of the batteries themselves. The positive electrode material has the greatest influence on the energy density of the whole battery system, and therefore, the research on the positive electrode material in the sodium-ion battery system is always in wide interest. Therefore, a positive electrode material having excellent performance is essential for a sodium ion battery.
In recent years, the research on interlayer compounds based on vanadium oxide xerogels has received much attention, since such compounds possess both the properties of vanadium oxides and of the embedded organic substances, a distinct feature of these compounds: are quasi-one-dimensional structures, and have a disordered structure similar to turbulence between layers, so that cations and organic molecules can be easily embedded into the structure. The characteristics of the vanadium sol are different from those of vanadium pentoxide crystals, the three-dimensional lattice of the vanadium pentoxide crystals can only allow the embedding of metal ions, the high holding capacity of the vanadium pentoxide crystals is determined by the properties of the polyvanadate crystals, and the high holding capacity of the vanadium pentoxide crystals is ensured by negative charges between layers of the polyvanadate crystals. The absorption, ion exchange or redox processes of the dipoles can produce ion intercalation, and in either case, the distance between the layers can change.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nanowire composite material (TPyP-V) prepared by doping vanadium pentoxide sol with porphyrin compound in the prior art2O5·nH2O) and a preparation method thereof, the synthesis process is simple, and the material has excellent performance in the electrochemical test of the sodium-ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: the nanometer line composite material of porphyrin compound doped vanadium pentoxide sol consists of TPyP-V in different lengths2O5·nH2The nano-wire is assembled, the width of the nano-wire is 80-100 nanometers, and the length of the nano-wire is 10-50 micrometers.
The preparation method of the nanowire composite material with the porphyrin compound doped with the vanadium pentoxide sol comprises the following steps:
1) adding a certain amount of vanadium pentoxide sol into deionized water for dilution, and then stirring to uniformly mix the solution;
2) adding 5,10,15, 20-tetra (4-pyridyl) porphyrin into dilute hydrochloric acid and stirring to obtain a mixed solution;
3) slowly dripping the solution obtained in the step 2) into the solution obtained in the step 1) to generate a precipitate, and then stirring the precipitate to fully react;
4) carrying out hydrothermal reaction on the solution obtained in the step 3);
5) cleaning the product obtained in the step 4) with acetone and alcohol, and drying in vacuum to obtain the nano-wire composite material of porphyrin compound doped with vanadium pentoxide sol.
According to the scheme, the amount of the vanadium pentoxide sol in the step 1) is 105mg, the deionized water is 20mL, the stirring time is 30min, the amount of the 5,10,15, 20-tetra (4-pyridyl) porphyrin in the step 2) is 5-30mg, and the stirring time is 30 min.
According to the scheme, the concentration of the dilute hydrochloric acid in the step 2) is 0.1 mol/L.
According to the scheme, the hydrothermal temperature in the step 4) is 180-200 ℃, and the hydrothermal time is 24-36 h.
The nanometer line composite material of the porphyrin compound doped with the vanadium pentoxide sol is applied as the anode material of the sodium ion battery.
The invention has the beneficial effects that: according to the unique molecular structure of 5,10,15, 20-tetra (4-pyridyl) porphyrin, after the molecular structure is embedded into vanadium pentoxide sol, hydrogen bonds can be formed between the vanadium pentoxide sol and vanadium pentoxide materials to form hydrogen bonds, so that the distance between vanadium pentoxide sol layers is enlarged, the stability of the structure is improved, the vanadium pentoxide sol is prepared by utilizing a melting-quenching method, and on the other hand, the crystallization degree of the materials is enhanced through hydrothermal treatment, so that the nano wire composite material of porphyrin compound doped vanadium pentoxide sol is obtained. The electrochemical performance of sodium ions is tested, and the result shows that the material has long service life, excellent cycle stability and rate capability when being used as the anode material of the sodium ion batteryCan be used. When the material is used as a positive electrode material of a sodium-ion battery, the concentration is 100mAg-1Under the current density of (2), after circulating for 100 circles, the specific discharge capacity is still as high as 150mAh g-1And excellent cycle performance is shown. At 1000mAg-1The constant current discharge test under the high current density shows that the discharge specific capacity is still kept at 100mAh g after 500 cycles of circulation-1And the better long-cycle performance is shown. The capacity retention rate is good when the multiplying power test is carried out on the material under different current densities. Test results show that the porphyrin compound doped vanadium pentoxide sol nanowire composite material can be used as a potential application material of a long-life, excellent cycle stability and high-magnification sodium ion battery anode material.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of the porphyrin-based compound doped vanadium pentoxide sol nanowire composite material in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the nano-wire composite material of the porphyrin compound doped with the vanadium pentoxide sol of embodiment 1 of the invention;
FIG. 3 shows that the nanowire composite material of porphyrin compound doped with vanadium pentoxide sol has a thickness of 100mAg in embodiment 1 of the present invention-1A battery cycle performance plot at current density;
FIG. 4 shows that the nanowire composite material prepared by doping porphyrin compound with vanadium pentoxide sol has a thickness of 1000mAg in embodiment 1 of the invention-1A battery cycle performance plot at current density;
fig. 5 is a battery cycle rate performance diagram of the porphyrin compound doped vanadium pentoxide sol nanowire composite material of embodiment 1 of the invention at different current densities.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
the preparation method of the nano-wire composite material of porphyrin compound doped with vanadium pentoxide sol comprises the following steps:
1) weighing a certain amount of vanadium pentoxide powder, putting the vanadium pentoxide powder into a high-temperature-resistant ceramic crucible, putting the crucible into a muffle furnace, quickly heating to 800 ℃, and preserving heat for 30 minutes.
2) Putting a certain amount of deionized water into a beaker, pouring the product obtained in the step 1) into the deionized water at normal temperature, putting the beaker into a water bath kettle, stirring until the solution is uniformly mixed, and cooling the solution to room temperature.
3) And filtering the cooled mixed solution for three times by using mesoporous and microporous filter paper respectively, taking supernatant, and standing to obtain the reddish brown vanadium pentoxide sol.
4) 105mg of the vanadium pentoxide sol was placed in a 50ml beaker, and 20ml of deionized water was added for dilution, followed by stirring for 30 minutes.
5) 0.1mL of concentrated hydrochloric acid is taken, 120mL of deionized water is added for dilution, stirring is carried out for 30 minutes, the mixture is uniformly mixed for later use, 15mg of 5,10,15, 20-tetra (4-pyridyl) porphyrin is weighed, added into 9mL of diluted hydrochloric acid, and stirring is carried out for 30 minutes.
6) Slowly dropping the solution obtained in the step 5) into the solution obtained in the step 4), and quickly generating dark green precipitates along with the dropping of the solution until all the solution is dropped, and then stirring the solution to fully react.
7) Putting the solution obtained in the step 6) into a reaction kettle, and putting the reaction kettle into a constant-temperature oven at 180 ℃ for hydrothermal reaction for 24 hours.
8) Repeatedly cleaning the product obtained in the step 7) with acetone and alcohol for three times, and drying in a vacuum drying oven at 60 ℃ to obtain the porphyrin compound doped vanadium pentoxide sol nanowire composite material (TPyP-V)2O5·nH2O)。
Taking the nano-wire composite material of the porphyrin compound doped with the vanadium pentoxide sol as an example, the structure of the nano-wire composite material is determined by an X-ray diffractometer. The diffraction peak position between layers of the vanadium pentoxide sol is about 10 degrees, as shown in figure 1, an X-ray diffraction pattern (XRD) shows that the characteristic peak shifts leftwards, and organic matters are well embedded between layers. As shown in FIG. 2, a Field Emission Scanning Electron Microscope (FESEM) test chartObviously, the width of the nanowire is about 100 nanometers, and the nanowire is composed of TPyP-V with different lengths2O5·nH2The O nanowires are assembled, and the length of the nanowires is about 10-50 microns.
The nano-wire composite material of the porphyrin compound doped with the vanadium pentoxide sol is used as the positive electrode active material of the sodium-ion battery. The preparation method of the electrode plate comprises the following steps of coating the nano-wire composite material of porphyrin compound doped with vanadium pentoxide sol as an active material, and punching the active material into a wafer by a punching machine for later use. A sodium sheet is used as a counter electrode, a glass fiber membrane is used as a diaphragm, and CR 2016 type stainless steel is used as a battery shell to assemble the button type sodium-ion battery. As shown in FIG. 3, at 100mAg-1The test is carried out under the current density, after the circulation is carried out for 100 circles, the specific discharge capacity is still as high as 150mAh g-1And excellent cycle performance is shown. As shown in FIG. 4, at 1000mAg-1Constant current discharge test is carried out under high current density, and the discharge specific capacity is still kept at 100mAh g after 500 cycles of circulation-1And the better long-cycle performance of the catalyst is embodied. As shown in fig. 5, the capacity retention rate was very good when the multiplying factor was measured at different current densities.
Example 2:
1) weighing a certain amount of vanadium pentoxide powder, putting the vanadium pentoxide powder into a high-temperature-resistant ceramic crucible, putting the crucible into a muffle furnace, quickly heating to 800 ℃, and preserving heat for 30 minutes.
2) Putting a certain amount of deionized water into a beaker, pouring the product obtained in the step 1) into the deionized water at normal temperature, putting the beaker into a water bath kettle, stirring until the solution is uniformly mixed, and cooling the beaker to the room temperature.
3) And filtering the cooled mixed solution for three times by using mesoporous and microporous filter paper respectively, taking supernatant, and standing to obtain the reddish brown vanadium pentoxide sol.
4) 105mg of the vanadium pentoxide sol was placed in a 50ml beaker, and 20ml of deionized water was added for dilution, followed by stirring for 30 minutes.
5) 0.1mL of concentrated hydrochloric acid is taken, 120mL of deionized water is added for dilution, stirring is carried out for 30 minutes, 5mg of 5,10,15, 20-tetra (4-pyridyl) porphyrin is weighed and added into 9mL of diluted hydrochloric acid, and stirring is carried out for 30 minutes.
6) Slowly dropping the solution obtained in the step 5) into the solution obtained in the step 4), and quickly generating dark green precipitates along with the dropping of the solution until all the solution is dropped, and then stirring the solution to fully react.
7) Putting the solution obtained in the step 6) into a reaction kettle, and putting the reaction kettle into a constant-temperature oven at 180 ℃ for hydrothermal reaction for 24 hours.
8) Repeatedly cleaning the product obtained in the step 7) with acetone and alcohol for three times, and drying in a vacuum drying oven at 60 ℃ to obtain the porphyrin compound doped vanadium pentoxide sol nanowire composite material (TPyP-V)2O5·nH2O)。
The product of the present invention is a nanowire having a width of about 100 nm. 100mAg of nanowire composite material prepared by doping vanadium pentoxide sol with porphyrin compound obtained in the example-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 40mAh g after 100 cycles-1。
Example 3:
1) weighing a certain amount of vanadium pentoxide powder, putting the vanadium pentoxide powder into a high-temperature-resistant ceramic crucible, putting the crucible into a muffle furnace, quickly heating to 800 ℃, and preserving heat for 30 minutes.
2) Putting a certain amount of deionized water into a beaker, pouring the product obtained in the step 1) into the deionized water at normal temperature, putting the beaker into a water bath kettle, stirring until the solution is uniformly mixed, and cooling the beaker to the room temperature.
3) And filtering the cooled mixed solution for three times by using mesoporous and microporous filter paper respectively, taking supernatant, and standing to obtain the reddish brown vanadium pentoxide sol.
4) 105mg of the vanadium pentoxide sol was placed in a 50ml beaker, and 20ml of deionized water was added for dilution, followed by stirring for 30 minutes.
5) 0.1mL of concentrated hydrochloric acid is taken, 120mL of deionized water is added for dilution, stirring is carried out for 30 minutes, the mixture is uniformly mixed for standby, 20mg of 5,10,15, 20-tetra (4-pyridyl) porphyrin is weighed, added into 9mL of diluted hydrochloric acid, and stirring is carried out for 30 minutes.
6) Slowly dropping the solution obtained in the step 5) into the solution obtained in the step 4), and quickly generating dark green precipitates along with the dropping of the solution until all the solution is dropped, and then stirring the solution to fully react.
7) Putting the solution obtained in the step 6) into a reaction kettle, and putting the reaction kettle into a constant-temperature oven at 180 ℃ for hydrothermal reaction for 24 hours.
8) Repeatedly cleaning the product obtained in the step 7) with acetone and alcohol for three times, and drying in a vacuum drying oven at 60 ℃ to obtain the porphyrin compound doped vanadium pentoxide sol nanowire composite material (TPyP-V)2O5·nH2O)。
The product of the present invention is a nanowire having a width of about 100 nm. Take the nanowire composite material of the porphyrin compound doped with the vanadium pentoxide sol obtained in the example as an example, 100mAg-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 130mAh g after 100 cycles-1。
Example 4:
1) weighing a certain amount of vanadium pentoxide powder, putting the vanadium pentoxide powder into a high-temperature-resistant ceramic crucible, putting the crucible into a muffle furnace, quickly heating to 800 ℃, and preserving heat for 30 minutes.
2) Putting a certain amount of deionized water into a beaker, pouring the product obtained in the step 1) into the deionized water at normal temperature, putting the beaker into a water bath kettle, stirring until the solution is uniformly mixed, and cooling the beaker to the room temperature.
3) And filtering the cooled mixed solution for three times by using mesoporous and microporous filter paper respectively, taking supernatant, and standing to obtain the reddish brown vanadium pentoxide sol.
4) 105mg of the vanadium pentoxide sol was placed in a 50ml beaker, and 20ml of deionized water was added for dilution, followed by stirring for 30 minutes.
5) 0.1mL of concentrated hydrochloric acid is taken, 120mL of deionized water is added for dilution, stirring is carried out for 30 minutes, 25mg of 5,10,15, 20-tetra (4-pyridyl) porphyrin is weighed and added into 9mL of diluted hydrochloric acid, and stirring is carried out for 30 minutes.
6) Slowly dropping the solution obtained in the step 5) into the solution obtained in the step 4), and quickly generating dark green precipitates along with the dropping of the solution until all the solution is dropped, and then stirring the solution to fully react.
7) Putting the solution obtained in the step 6) into a reaction kettle, and putting the reaction kettle into a constant-temperature oven at 180 ℃ for hydrothermal reaction for 24 hours.
8) Repeatedly cleaning the product obtained in the step 7) with acetone and alcohol for three times, and drying in a vacuum drying oven at 60 ℃ to obtain the porphyrin compound doped vanadium pentoxide sol nanowire composite material (TPyP-V)2O5·nH2O)。
The product of the present invention is a nanowire having a width of about 100 nm. 100mAg of nanowire composite material prepared by doping vanadium pentoxide sol with porphyrin compound obtained in the example-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 120mAh g after 100 cycles-1。
Example 5:
1) weighing a certain amount of vanadium pentoxide powder, putting the vanadium pentoxide powder into a high-temperature-resistant ceramic crucible, putting the crucible into a muffle furnace, quickly heating to 800 ℃, and preserving heat for 30 minutes.
2) Putting a certain amount of deionized water into a beaker, pouring the product obtained in the step 1) into the deionized water at normal temperature, putting the beaker into a water bath kettle, stirring until the solution is uniformly mixed, and cooling the beaker to the room temperature.
3) And filtering the cooled mixed solution for three times by using mesoporous and microporous filter paper respectively, taking supernatant, and standing to obtain the reddish brown vanadium pentoxide sol.
4) 105mg of the vanadium pentoxide sol was placed in a 50ml beaker, and 20ml of deionized water was added for dilution, followed by stirring for 30 minutes.
5) 0.1mL of concentrated hydrochloric acid is taken, 120mL of deionized water is added for dilution, stirring is carried out for 30 minutes, the mixture is uniformly mixed for standby, 30mg of 5,10,15, 20-tetra (4-pyridyl) porphyrin is weighed, added into 9mL of diluted hydrochloric acid, and stirring is carried out for 30 minutes.
6) Slowly dropping the solution obtained in the step 5) into the solution obtained in the step 4), and quickly generating dark green precipitates along with the dropping of the solution until all the solution is dropped, and then stirring the solution to fully react.
7) Putting the solution obtained in the step 6) into a reaction kettle, and putting the reaction kettle into a constant-temperature oven at 180 ℃ for hydrothermal reaction for 24 hours.
8) Repeatedly cleaning the product obtained in the step 7) with acetone and alcohol for three times, and drying in a vacuum drying oven at 60 ℃ to obtain the porphyrin compound doped vanadium pentoxide sol nanowire composite material (TPyP-V)2O5·nH2O)。
The product of the present invention is a nanowire having a width of about 100 nm. The nanowire composite material prepared by doping vanadium pentoxide sol with porphyrin compound obtained in the example is 100mA g-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 110mAh g after 100 cycles-1。

Claims (4)

1. The preparation method of the nanowire composite material of the porphyrin compound doped vanadium pentoxide sol comprises the step of preparing TPyP-V with different lengths2O5·nH2The method is characterized in that the O nanowire is assembled, the width of the nanowire is 80-100 nanometers, the length of the nanowire is 10-50 micrometers, and the method comprises the following steps:
1) adding a certain amount of vanadium pentoxide sol into deionized water for dilution, and then stirring to uniformly mix the solution; the amount of the vanadium pentoxide sol is 105mg, the deionized water is 20mL, and the stirring time is 30 min;
2) adding 5,10,15, 20-tetra (4-pyridyl) porphyrin into dilute hydrochloric acid and stirring to obtain a mixed solution; 15mg of 5,10,15, 20-tetra (4-pyridyl) porphyrin is stirred for 30 min;
3) slowly dripping the solution obtained in the step 2) into the solution obtained in the step 1) to generate a precipitate, and then stirring the precipitate to fully react;
4) carrying out hydrothermal reaction on the solution obtained in the step 3);
5) cleaning the product obtained in the step 4) with acetone and alcohol, and drying in vacuum to obtain the nano-wire composite material of porphyrin compound doped with vanadium pentoxide sol.
2. The method for preparing a nanowire composite material of a porphyrin compound doped with vanadium pentoxide sol according to claim 1, wherein the concentration of the dilute hydrochloric acid in the step 2) is 0.1 mol/L.
3. The method for preparing a nanowire composite material doped with vanadium pentoxide sol according to claim 1, wherein the hydrothermal temperature in step 4) is 180-200 ℃ and the hydrothermal time is 24-36 h.
4. The application of the composite material obtained by the preparation method of the nano-wire composite material of porphyrin compound doped vanadium pentoxide sol of claim 1 as the positive electrode material of a sodium-ion battery.
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