CN115726059A - Ammonium borate modified carbon-based nanofiber composite material and preparation method and application thereof - Google Patents
Ammonium borate modified carbon-based nanofiber composite material and preparation method and application thereof Download PDFInfo
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- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims abstract description 47
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Carbon And Carbon Compounds (AREA)
Abstract
In order to further improve the adsorption-intercalation effect of the existing carbon-based nano-fiber composite material on lithium/sodium ions, the invention provides an ammonium borate modified carbon-based nano-fiber composite material and a preparation method and application thereof, wherein the preparation method of the ammonium borate modified carbon-based nano-fiber composite material comprises the following steps: dissolving a high molecular polymer in an organic solvent to prepare a precursor solution; performing electrostatic spinning on the precursor solution to prepare a nanofiber precursor film; pre-oxidizing the nanofiber precursor film; and (3) soaking the pre-oxidized nanofiber precursor film in an ammonium borate solution, taking out, drying and carbonizing to obtain the ammonium borate modified carbon-based nanofiber composite material.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to an ammonium borate modified carbon-based nano fiber composite material as well as a preparation method and application thereof.
Background
With the large-scale development of industry and commerce, the energy demand is increasingly urgent, and the traditional energy supply and use mode can not completely meet the actual production and life gradually, so the development of the new energy field is on the rise from product development to market application. Among them, lithium/sodium ion batteries used in new energy have been widely used in various fields such as power cars, household portable devices, information technologies, and the like, because of their advantages of high energy density, excellent cycle stability, long service life, no memory effect, and environmental friendliness.
Currently, lithium ion batteries are facing adverse factors such as high price of raw materials and poor domestic mineral resources, so that a necessary trend is to search for novel batteries with lower cost and rich domestic storage. At present, the materials applied to the negative electrode of the lithium ion battery are usually graphite materials, including natural graphite and artificial graphite, but the graphite materials cannot be normally used in the sodium ion battery, because the radius of sodium ions is larger than that of lithium ions, and the large volume expansion is caused by the deintercalation in the graphite materials, so that the structure of the negative electrode is damaged, and the cycle life is greatly shortened.
Different from graphite cathode materials, the carbon nanofiber material with heteroatom doping can be used as an excellent lithium/sodium ion battery cathode material to realize uniform adsorption and desorption of lithium/sodium ions on the surface of a cathode. In the prior art CN114335524, the heteroatom-doped porous carbon nanobelt material is spun by mixing a water-soluble precursor solution with a doping compound to obtain a carbon nanofiber membrane, but the method is limited by the compatibility between the precursor solution and the doping compound.
The patent with the application number of 201810621963.1 discloses B and N double-doped carbon aerogel based on methylcellulose and a preparation method thereof, the methylcellulose can form self-crosslinking hydrogel, the hydrogel takes a doping agent ammonium borate solution as a solvent, and a carbon aerogel material with a three-dimensional porous network structure is obtained through drying and carbonization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ammonium borate modified carbon-based nanofiber composite material, and a preparation method and application thereof, and further improves the adsorption-intercalation effect of the carbon-based nanofiber composite material on lithium/sodium ions.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of an ammonium borate modified carbon-based nanofiber composite material, which comprises the following operation steps:
dissolving a high molecular polymer in an organic solvent to prepare a precursor solution;
performing electrostatic spinning on the precursor solution to prepare a nanofiber precursor film;
pre-oxidizing the nanofiber precursor film;
and (3) soaking the pre-oxidized nanofiber precursor film in an ammonium borate solution, taking out, drying and carbonizing to obtain the ammonium borate modified carbon-based nanofiber composite material.
Optionally, the mass fraction of the high molecular polymer is 6% to 12% based on 100% of the mass of the precursor solution.
Optionally, the concentration of the ammonium borate solution is 0.02-0.15mol/L.
Optionally, the high molecular polymer includes one or more of polyacrylonitrile, polyvinylpyrrolidone, polypyrrole, polyaniline, polythiophene and polyvinyl alcohol;
the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
Optionally, the electrostatic spinning process conditions include: spinning voltage is 10-20kV, receiving distance is 10-18cm, advancing speed is 0.2-0.5mL/h, spinning environment temperature is 20-40 ℃, and environment humidity is 15-60RH%.
Optionally, the pre-oxidation conditions are: the pre-oxidation temperature is 220-280 ℃, and the pre-oxidation time is 1-4h.
Optionally, the time for soaking the pre-oxidized nanofiber precursor film in the ammonium borate solution is 20-36h;
the drying conditions are as follows: the drying temperature is 50-80 ℃, and the drying time is 6-12h.
Optionally, the carbonization treatment process includes: and heating the dried nanofiber precursor film to 600-1000 ℃ at the heating rate of 1-5 ℃/min under the protective atmosphere, and preserving the heat for 1-3h.
On the other hand, the invention also provides an ammonium borate modified carbon-based nanofiber composite material, which is prepared by any one of the preparation methods of the ammonium borate modified carbon-based nanofiber composite material, wherein the micro-morphology of the ammonium borate modified carbon-based nanofiber composite material is in a three-dimensional cross-linked network structure, and boron and nitrogen are co-doped in the carbon-based nanofibers.
On the other hand, the invention also provides application of the ammonium borate modified carbon-based nanofiber composite material in a battery cathode or in a fast-charging lithium/sodium ion battery.
According to the preparation method of the ammonium borate modified carbon-based nanofiber composite material, provided by the invention, the ammonium borate modified carbon-based nanofiber material is obtained by taking a carbon-containing high-molecular polymer as a carbon source and combining a doping mode of dipping in an ammonium borate solution. The preparation method is simple to operate, green and environment-friendly, and the used raw materials are wide in source and low in cost, so that the preparation method is more suitable for wide production. By dipping the nanofiber precursor film in the ammonium borate solution, the problem of the compatibility of the precursor solution and the doping compound is solved.
The ammonium borate modified carbon-based nanofiber material has a rich conductive network structure inside, and can effectively improve the electron and ion conduction capacity, so that the material can be used as a negative electrode material in the application of a sodium ion battery, and also has the function of serving as a current collector in a battery component. Therefore, in the construction process of the lithium/sodium ion battery, the ammonium borate modified carbon-based nanofiber composite material is used as a self-supporting negative electrode, so that the use of a metal foil originally used as a current collector, a corresponding binder and a conductive agent can be effectively omitted, the manufacturing cost of the battery is favorably reduced, and the overall energy density of the battery is improved.
Boron and nitrogen doping modification is carried out on the carbon-based nanofiber by adopting an ammonium borate solution dipping mode, so that defect sites of the nanofiber are obviously increased, the adsorption effect of the nanofiber as a negative electrode material on lithium/sodium ions is favorably improved, the carbon layer spacing of the modified carbon-based nanofiber is enlarged, and the desorption-intercalation of the lithium/sodium ions and the storage in a carbon material in the charging and discharging process are favorably realized.
Drawings
FIG. 1 is a scanning electron microscope image of a carbon-based nanofiber material prepared in comparative example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the ammonium borate modified carbon-based nanofiber material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the ammonium borate modified carbon-based nanofiber material prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of an ammonium borate modified carbon-based nanofiber material prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of the ammonium borate modified carbon-based nanofiber material prepared in example 4 of the present invention;
FIG. 6 is an XRD pattern of ammonium borate modified carbon based nanofiber materials prepared in comparative example 1 and examples 1-4 of the present invention;
FIG. 7 is a Raman plot of ammonium borate modified carbon based nanofiber materials prepared in comparative example 1 and examples 1-3 of the present invention;
FIG. 8 is a battery AC impedance profile of the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1-4 of the present invention for testing of a sodium ion battery negative electrode;
FIG. 9 is a graph of battery cycle performance for testing the use of ammonium borate modified carbon-based nanofiber materials prepared in comparative example 1 and examples 1-4 of the present invention as negative electrodes of sodium ion batteries;
FIG. 10 is a scanning electron microscope image of an ammonium borate modified carbon-based nanofiber material prepared in example 7 of the present invention;
FIG. 11 is a scanning electron microscope image of an ammonium borate modified carbon-based nanofiber material prepared in example 8 of the present invention;
FIG. 12 is an XRD pattern of ammonium borate modified carbon based nanofiber materials prepared in examples 1, 7 and 8 of the present invention;
fig. 13 is a battery cycle performance graph of the ammonium borate modified carbon-based nanofiber material prepared in example 1, example 7 and example 8 of the present invention used as a negative electrode test of a sodium ion battery.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The embodiment of the invention provides a preparation method of an ammonium borate modified carbon-based nanofiber composite material, which comprises the following operation steps:
dissolving a high molecular polymer in an organic solvent to prepare a precursor solution;
performing electrostatic spinning on the precursor solution to prepare a nanofiber precursor film;
pre-oxidizing the nanofiber precursor film, specifically, pre-oxidizing in air;
and (3) soaking the pre-oxidized nanofiber precursor film in an ammonium borate solution, taking out, drying and carbonizing to obtain the ammonium borate modified carbon-based nanofiber composite material.
In this embodiment, in the preparation method of the ammonium borate modified carbon-based nanofiber composite, the carbon-containing high molecular polymer is used as a carbon source, and a doping manner of dipping in an ammonium borate solution is combined to obtain the ammonium borate modified carbon-based nanofiber material. The preparation method is simple to operate, green and environment-friendly, and the used raw materials are wide in source and low in cost, so that the preparation method is more suitable for wide production.
The ammonium borate modified carbon-based nanofiber material has a rich conductive network structure inside, and can effectively improve the electron and ion conduction capacity, so that the material can be used as a negative electrode material in the application of a sodium ion battery, and also has the function of serving as a current collector in a battery component. Therefore, in the construction process of the lithium/sodium ion battery, the ammonium borate modified carbon-based nanofiber composite material is used as a self-supporting negative electrode, so that the use of a metal foil which is originally used as a current collector, a corresponding binder and a conductive agent can be effectively omitted, the manufacturing cost of the battery can be reduced, and the overall energy density of the battery can be improved.
Boron and nitrogen doping modification is carried out on the carbon-based nanofiber by adopting an ammonium borate solution dipping mode, so that the defect sites of the nanofiber are obviously increased, the adsorption effect of the nanofiber as a negative electrode material on lithium/sodium ions is favorably improved, the carbon layer spacing of the modified carbon-based nanofiber is expanded, and the desorption-intercalation of the lithium/sodium ions and the storage in a carbon material in the charging and discharging process are favorably realized.
In some embodiments, the high molecular polymer has a mass fraction of 6% to 12% based on 100% by mass of the precursor solution.
In some embodiments, the concentration of the ammonium borate solution is 0.02 to 0.15mol/L. Specifically, the concentration of the ammonium borate solution may be any one of 0.02mol/L, 0.03mol/L, 0.05mol/L, 0.07mol/L, 0.10mol/L, 0.12mol/L, and 0.15mol/L.
In some embodiments, the high molecular weight polymer includes one or more of polyacrylonitrile, polyvinylpyrrolidone, polypyrrole, polyaniline, polythiophene, and polyvinyl alcohol.
The organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
In some embodiments, the process conditions of electrospinning comprise: spinning voltage is 10-20kV, receiving distance is 10-18cm, advancing speed is 0.2-0.5mL/h, spinning environment temperature is 20-40 ℃, and environment humidity is 15-60RH%.
In some embodiments, the pre-oxidation conditions are: the pre-oxidation temperature is 220-280 ℃, and the pre-oxidation time is 1-4h.
In some embodiments, the pre-oxidized nanofiber precursor film is immersed in the ammonium borate solution for a period of 20 to 36 hours.
The drying conditions are as follows: the drying temperature is 50-80 ℃, and the drying time is 6-12h.
In some embodiments, the carbonization process is: and heating the dried nanofiber precursor film to 600-1000 ℃ at the heating rate of 1-5 ℃/min under the protective atmosphere, and preserving the heat for 1-3h. Specifically, the protective atmosphere is nitrogen, argon, or hydrogen.
On the other hand, an embodiment of the invention further provides an ammonium borate modified carbon-based nanofiber composite material, which is prepared by any one of the preparation methods of the ammonium borate modified carbon-based nanofiber composite material, wherein the micro-morphology of the ammonium borate modified carbon-based nanofiber composite material is in a three-dimensional cross-linked network structure, and boron and nitrogen are co-doped in carbon-based nanofibers.
On the other hand, an embodiment of the invention also provides application of the ammonium borate modified carbon-based nanofiber composite material in a battery cathode or in a fast-charging lithium/sodium ion battery.
The present invention is further illustrated by the following examples.
Example 1
This example is used to illustrate a method for preparing an ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes the following steps:
1) Dissolving polyacrylonitrile in an N, N-dimethylformamide solvent, and stirring vigorously to prepare a transparent polymer precursor solution with the mass volume ratio of 10%;
2) Preparing the spinning solution into a polymer nanofiber film by adopting an electrostatic spinning method, wherein the electrostatic spinning process parameters are as follows: the spinning voltage is 10kV, the advancing speed of the spinning solution is 0.5mL/h, the spinning receiving distance is 15cm, the spinning environment temperature is 25 ℃, and the environment humidity is 40RH%;
3) Pre-oxidizing the obtained nanofiber membrane for 2h at 260 ℃ in the air atmosphere to obtain a pre-oxidized nanofiber membrane;
4) Soaking the pre-oxidized nanofiber membrane in an ammonium borate solution with the concentration of 0.02mol/L for 24 hours, and then drying the membrane at 60 ℃ for 8 hours to obtain a 0.02mol/L ammonium borate soaked nanofiber membrane;
5) And (3) placing the obtained ammonium borate dipped nanofiber film into a tubular furnace, and carrying out heat treatment for 1h at 600 ℃ in a protective atmosphere at the heating rate of 5 ℃/min to obtain the ammonium borate modified carbon-based nanofiber material.
Example 2
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, except that: the concentration of the ammonium borate solution was 0.05mol/L.
Example 3
This example is intended to illustrate a method for preparing an ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, with the following differences: the concentration of the ammonium borate solution was 0.1mol/L.
Example 4
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, except that: the concentration of the ammonium borate solution was 0.15mol/L.
Example 5
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, except that: the mass fraction of the polymer in the precursor solution was 8%.
Example 6
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, except that: the mass fraction of the polymer in the precursor solution was 12%.
Example 7
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, except that:
the carbonization conditions are as follows: heat treatment at 800 deg.C for 1h.
Example 8
This example is intended to illustrate a method for preparing an ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, with the following differences:
the carbonization conditions are as follows: heat treatment is carried out for 1h at 1000 ℃.
Example 9
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 2, except that:
the pre-oxidation time is 4 hours, the concentration of the ammonium borate solution is 0.05mol/L, the pre-oxidized nanofiber membrane is soaked in the ammonium borate solution for 20 hours, and then the nanofiber membrane is taken out and dried at 50 ℃ for 10 hours;
the carbonization conditions are as follows: heat treatment is carried out for 3h at 600 ℃, and the heating rate is 3 ℃/min.
Example 10
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 3, except that:
the pre-oxidation conditions are as follows: pre-oxidizing at 240 ℃ for 3h, wherein the concentration of an ammonium borate solution is 0.1mol/L, soaking the pre-oxidized nanofiber membrane in the ammonium borate solution for 36h, and then drying at 80 ℃ for 6h;
the carbonization conditions are as follows: heat treatment is carried out for 2h at 600 ℃, and the heating rate is 3 ℃/min.
Example 11
This example is used to illustrate the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 4, except that: the mass fraction of the polymer in the precursor solution is 6%, and the pre-oxidation conditions are as follows: pre-oxidizing at 280 ℃ for 1h, wherein the concentration of an ammonium borate solution is 0.15mol/L, soaking the pre-oxidized nanofiber membrane in the ammonium borate solution for 30h, and then drying at 80 ℃ for 12h;
the carbonization conditions are as follows: heat treatment is carried out for 1h at 600 ℃, and the heating rate is 2 ℃/min.
Comparative example 1
This comparative example is used for comparative illustration of the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and includes most of the operation steps in example 1, and the differences are that: and (3) placing the preoxidized nanofiber membrane into a tubular furnace, and carrying out heat treatment for 1h at 600 ℃ in a protective atmosphere at the heating rate of 5 ℃/min to obtain the carbon-based nanofiber material.
The advantageous effects of the present invention are further illustrated by the tests below.
Cutting the prepared carbon-based nanofiber film into a wafer with the diameter of 12mm, cleaning the wafer with alcohol, putting the wafer into a vacuum drying oven, and directly using the wafer as a self-supporting cathode after vacuum drying for 24 hours at 70 ℃. And putting the dried self-supporting cathode material into a glove box, and assembling the self-supporting cathode material into a 2032 type button cell for subsequent electrochemical performance test. Wherein the AC impedance test condition is 0.01Hz-100kHz, and the cycle performance test condition is 100mA g -1 And carrying out constant current charge and discharge test with the current density between 0 and 3.0V.
The prepared carbon-based nanofiber film was subjected to phase analysis, and the analysis results are shown in the following table:
TABLE 1
According to the electrochemical performance tests of the embodiment 1-embodiment 11, the ammonium borate modified carbon nanofiber prepared by the method disclosed by the invention is used as a self-supporting negative electrode material for a sodium ion battery, so that the excellent specific discharge capacity and the excellent cycling stability are shown, and after 100-week charge-discharge cycling, the reversible charge-discharge specific capacity of the battery can reach 315.6mAh/g, so that the ammonium borate modified carbon nanofiber has a wide application prospect.
Comparing the scanning electron micrographs of the obtained comparative example 1 and examples 1 to 4 samples of fig. 1 to 5 simultaneously, it was found that the nanofiber surface gradually became rough by the impregnation with ammonium borate due to decomposition of NH from the impregnated ammonium borate during the heat treatment 3 Has the function of making pores, thereby forming a porous structure and enhancing the surface activity of the material. The fiber membrane can effectively adsorb lithium/sodium ions when being used as a self-supporting cathode of the battery, so that the overall working efficiency and the service life of the battery are improved. However, as the impregnation concentration of ammonium borate increased, some micro cracks gradually appeared on the surface of the 0.10mol/L ammonium borate modified carbon-based nanofiber film presented in fig. 4, while a larger area of carbon nanofiber was broken on the surface of the 0.15mol/L ammonium borate modified carbon-based nanofiber film obtained in fig. 5. Meanwhile, with the increase of the impregnation concentration of the ammonium borate, the brittleness of each obtained ammonium borate modified carbon-based nanofiber film is increased macroscopically. The above results indicate that moderate impregnation of ammonium borate is beneficial to maintain the toughness of the self-supporting anode material, and that excessive impregnation is not beneficial to relieve the volume expansion generated during the metal ion deintercalation process, so the concentration of ammonium borate is preferably 0.02-0.10mol/L.
Fig. 6 is an XRD pattern of the ammonium borate-modified carbon-based nanofiber materials prepared in comparative example 1 and examples 1 to 4, and it can be seen from fig. 6 that only graphitized carbon peaks exist in the XRD diffraction pattern and other characteristic peaks are not shown when the impregnation concentration of ammonium borate is low (0.02 and 0.05 mol/L). Whereas at higher ammonium borate impregnation concentrations (0.10 and 0.15 mol/L) a crystallization peak occurred at 28.1 °, comparing PDF cards presumably due to crystallization of the fiber film to some B-containing crystals due to excessive ammonium borate solution concentrations. Meanwhile, as the impregnation concentration of ammonium borate increased, the carbon-layer spacings of the respective samples were 0.390 (comparative example 1), 0.388 (example 1), 0.391 (example 2), 0.393 (example 3), respectively, which indicates that after the impregnation of ammonium borate, the carbon nanofibers were doped with boron nitrogen atoms, resulting in a decrease in the carbon-layer spacings, but as the doping concentration increased, the layer spacings were larger than the undoped fiber films, instead.
FIG. 7 is a Raman spectrum of ammonium borate modified carbon-based nanofiber materials prepared in comparative example 1 and examples 1-3, showing a D peak (1350 cm) in the Raman spectrum of all samples -1 Indicating the degree of defect) and G peak (1580 cm -1 Indicating the degree of graphitization). As can be seen from the calculation of the peak intensity values (ID/IG) of the respective samples, the ID/IG values of the samples obtained in comparative example 1 and examples 1 to 3 were 1.05, 1.48, 1.41 and 1.41, respectively, indicating that the defect degree of the carbon nanofiber films impregnated with the 0.02mol/L ammonium borate solution was relatively high.
Fig. 8 is a battery ac impedance spectrum of the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1 to 4, which is used as a negative electrode of a sodium ion battery for testing, and as can be seen from the graph and table 1, the resistances of the sodium ion battery assembled by the carbon-based nanofiber self-supporting negative electrodes prepared in comparative example 1 and examples 1 to 4 in the middle frequency region are respectively: 501.2, 299.4, 378.7, 146.5 and 200.4. Compared with a sample which is not modified by ammonium borate, the method has the following advantages: (1) The carbon-based nano-fiber is modified by ammonium borate, so that the carbon-based material is doped and modified by B and N atoms, and the electron and ion conduction capability of the self-supporting cathode of the carbon-based nano-fiber is favorably improved; (2) Along with the increase of the impregnation concentration of ammonium borate, the impedance of a battery formed by the modified carbon-based nanofiber self-supporting negative electrode tends to decrease, and the analysis of the raman characterization result (shown in fig. 7) of the bonding material shows that the conductivity of the carbon material is enhanced by introducing more B and N atoms.
FIG. 9 is a graph of battery cycle performance for testing the ammonium borate modified carbon-based nanofiber materials prepared in comparative example 1 and examples 1-4 as negative electrodes of sodium ion batteries at a current density of 100mA g -1 Under the conditions of (a). Fig. 9 in conjunction with table 1, it can be seen that a moderate concentration of ammonium borate (0.02 mol/L ammonium borate impregnation) modification can be carbon compared to the carbon nanofiber membrane anode prepared in comparative example 1The self-supporting negative electrode material introduces abundant defect sites, so that the adsorption of the negative electrode to sodium ions is enhanced, the embedding and the separation of the sodium ions are facilitated, meanwhile, the suitable interlayer spacing of the carbon material possibly helps to form a sufficient closed pore structure, the storage of the sodium ions is promoted, and the initial capacity and the cycling stability of the battery are promoted to a large extent. With the increase of the concentration of ammonium borate, the doping content of B and N atoms is further increased, the introduced defects are greatly reduced, and the enlargement of interlayer spacing possibly causes the defect of closed pores, so that the initial discharge capacity of the sodium-ion battery formed by the atoms is reduced.
Fig. 12 is XRD patterns of samples of examples 1, 7 and 8 prepared by using different heat treatment temperatures, from which it can be seen that all samples have only typical carbon peaks, and from fig. 1, 10 and 11, the ammonium borate modified carbon-based nanofiber materials obtained in examples 1, 7 and 8 have carbon layer spacings of 0.388, 0.386 and 0.383nm, respectively, indicating that the material layer spacing decreases with increasing heat treatment temperature.
FIG. 13 is a graph of battery cycle performance for the ammonium borate modified carbon based nanofiber materials prepared in examples 1, 7 and 8 used as a sodium ion battery negative electrode test at a current density of 100mA g -1 Under the conditions of (1). As can be seen from the figures, all samples had good cycle stability, but the initial discharge capacity of the battery showed a tendency to gradually decrease as the heat treatment temperature was increased during the preparation of the samples, which may be due to the decrease in the carbon layer spacing caused by the increase in temperature, and the pore structure was not favorable for the intercalation of metal ions. Therefore, it can be seen that the heat treatment temperature for carbonization is preferably 600 to 800 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the ammonium borate modified carbon-based nanofiber composite material is characterized by comprising the following steps of:
dissolving a high molecular polymer in an organic solvent to prepare a precursor solution;
performing electrostatic spinning on the precursor solution to prepare a nanofiber precursor film;
pre-oxidizing the nanofiber precursor film;
and (3) soaking the pre-oxidized nanofiber precursor film in an ammonium borate solution, taking out, drying and carbonizing to obtain the ammonium borate modified carbon-based nanofiber composite material.
2. The method for preparing the ammonium borate modified carbon-based nanofiber composite material according to claim 1, wherein the mass fraction of the high molecular polymer is 6% -12% based on 100% of the mass of the precursor solution.
3. The method of preparing an ammonium borate modified carbon-based nanofiber composite of claim 1, wherein the concentration of the ammonium borate solution is 0.02-0.15mol/L.
4. The method of preparing an ammonium borate modified carbon-based nanofiber composite of claim 1, wherein the high molecular weight polymer comprises one or more of polyacrylonitrile, polyvinylpyrrolidone, polypyrrole, polyaniline, polythiophene, and polyvinyl alcohol;
the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
5. The method of preparing an ammonium borate modified carbon-based nanofiber composite of claim 1, wherein the electrospinning process conditions comprise: spinning voltage is 10-20kV, receiving distance is 10-18cm, advancing speed is 0.2-0.5mL/h, spinning temperature is 20-40 ℃, and ambient humidity is 15-60RH%.
6. The method of preparing an ammonium borate modified carbon-based nanofiber composite of claim 1, wherein the pre-oxidation conditions are: the pre-oxidation temperature is 220-280 ℃, and the pre-oxidation time is 1-4h.
7. The method for preparing the ammonium borate modified carbon-based nanofiber composite material according to claim 1, wherein the time for soaking the pre-oxidized nanofiber precursor film in the ammonium borate solution is 20-36h;
the drying conditions are as follows: the drying temperature is 50-80 ℃, and the drying time is 6-12h.
8. The method for preparing the ammonium borate modified carbon-based nanofiber composite material according to claim 7, wherein the carbonization treatment process comprises: and heating the dried nanofiber precursor film to 600-1000 ℃ at the heating rate of 1-5 ℃/min under the protective atmosphere, and preserving the heat for 1-3h.
9. The ammonium borate modified carbon-based nanofiber composite material is characterized by being prepared by the preparation method of the ammonium borate modified carbon-based nanofiber composite material according to any one of claims 1 to 8, wherein the micro-morphology of the ammonium borate modified carbon-based nanofiber composite material is in a three-dimensional cross-linked network-like structure, and boron and nitrogen are co-doped in carbon-based nanofibers.
10. Use of the ammonium borate modified carbon-based nanofiber composite of claim 9 in a battery negative electrode or in a fast-charging lithium/sodium ion battery.
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