CN115726059B - 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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- 239000002121 nanofiber Substances 0.000 title claims abstract description 121
- -1 Ammonium borate modified carbon Chemical class 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000009987 spinning Methods 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012528 membrane Substances 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 13
- 239000010405 anode material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- 239000002134 carbon nanofiber Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 230000002687 intercalation Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000007770 graphite material Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
In order to further improve the adsorption-intercalation effect of the existing carbon-based nanofiber composite material on lithium/sodium ions, the invention provides an ammonium borate modified carbon-based nanofiber composite material, and a preparation method and application thereof, wherein the preparation method of the ammonium borate modified carbon-based nanofiber composite material comprises the following steps: dissolving a high molecular polymer in an organic solvent to prepare a precursor solution; carrying out electrostatic spinning on the precursor solution to obtain a nanofiber precursor film; pre-oxidizing the nanofiber precursor film; immersing the pre-oxidized nanofiber precursor film in an ammonium borate solution, and then taking out the film for 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 nanofiber composite material, and a preparation method and application thereof.
Background
Along with the large-scale development of industry and commerce, the energy demand is urgent, and the traditional energy supply and use mode cannot fully meet the actual production and life gradually, so that the development of new energy fields from product development to market application is on the day of steaming. The lithium/sodium ion battery used in the new energy source has been widely used in various fields such as power automobiles, household portable equipment, information technology and the like due to the advantages of high energy density, excellent cycle stability, long service life, no memory effect, environmental protection and the like.
Currently, lithium ion batteries are facing adverse factors such as gradually increasing raw material prices, poor domestic mineral resources and the like, so that the search for novel batteries with lower cost and rich domestic storage becomes a necessary trend. At present, materials applied to a lithium ion battery cathode are usually graphite materials, including natural graphite and artificial graphite, but the materials cannot be normally used in a sodium ion battery because sodium ions have larger radius than lithium ions, and the intercalation and deintercalation in the graphite materials can cause larger volume expansion, so that the cathode structure is damaged, and the cycle life is greatly reduced.
Different from a graphite anode material, the carbon nanofiber material with heteroatom doping can be used as an excellent anode material of a lithium/sodium ion battery, and uniform adsorption and deintercalation of lithium/sodium ions on the surface of the anode are realized. In the prior art CN114335524, the heteroatom doped porous carbon nanoribbon material is spun after mixing the water soluble precursor solution with the dopant compound to obtain the carbon nanofiber membrane, but the method is limited by the compatibility of the precursor solution and the dopant compound.
Patent application number 201810621963.1 discloses a B, N double-doped carbon aerogel based on methyl cellulose and a preparation method thereof, wherein the methyl cellulose can form self-crosslinked hydrogel, the hydrogel takes an ammonium borate solution as a doping agent as a solvent, and the self-crosslinked hydrogel is dried and carbonized to obtain a carbon aerogel material with a three-dimensional porous network structure, and the preparation method does not need to consider the compatibility of a matrix and a doping compound, but needs to carry out freeze drying technology to shape the material, so that the preparation process is complex and is not beneficial to large-scale production.
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;
carrying out electrostatic spinning on the precursor solution to obtain a nanofiber precursor film;
Pre-oxidizing the nanofiber precursor film;
immersing the pre-oxidized nanofiber precursor film in an ammonium borate solution, and then taking out the film for 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% -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 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.
Optionally, the process conditions of the electrospinning include: the spinning voltage is 10-20kV, the receiving distance is 10-18cm, the propelling speed is 0.2-0.5mL/h, the spinning environment temperature is 20-40 ℃, and the 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 pre-oxidized nanofiber precursor film is immersed in the ammonium borate solution for 20-36 hours;
The drying conditions are as follows: the drying temperature is 50-80 ℃ and the drying time is 6-12h.
Optionally, the carbonization treatment process is as follows: heating the dried nanofiber precursor film to 600-1000 ℃ at a heating rate of 1-5 ℃/min under a protective atmosphere, and preserving 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 the preparation method of any ammonium borate modified carbon-based nanofiber composite material, wherein the microscopic morphology of the ammonium borate modified carbon-based nanofiber composite material is of a three-dimensional cross-linked network structure, and boron and nitrogen are co-doped in 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, the carbon-containing high molecular polymer is used as a carbon source, and the doping mode of dipping in ammonium borate solution is combined, so that the ammonium borate modified carbon-based nanofiber material is obtained. The preparation method is simple to operate, environment-friendly, wide in sources of raw materials, low in cost and more suitable for wide production. The problem of compatibility of the precursor solution with the dopant compound is solved by immersing the nanofiber precursor film in an ammonium borate solution.
The ammonium borate modified carbon-based nanofiber material has a rich conductive network structure in the interior, and can effectively improve the electronic and ionic conductivity, so that the material can be used as a negative electrode material and also has the function of being used as a current collector in a battery component in sodium ion battery application. 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 can be reduced, and the overall energy density of the battery can be improved.
The carbon-based nanofiber is modified by doping boron and nitrogen in an ammonium borate solution impregnation mode, so that defect sites of the nanofiber are remarkably increased, the adsorption effect of the anode material on lithium/sodium ions is improved, the carbon layer spacing of the modified carbon-based nanofiber is enlarged, and the deintercalation-intercalation of lithium/sodium ions and the storage of the carbon material in the charge-discharge process are facilitated.
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 an ammonium borate modified carbon-based nanofiber material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of an 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 an ammonium borate modified carbon-based nanofiber material prepared in example 4 of the present invention;
FIG. 6 is an XRD pattern of the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1 to 4 of the present invention;
FIG. 7 is a Raman diagram of the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1-3 of the present invention;
FIG. 8 is a graph showing the AC impedance of a battery using the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1-4 of the present invention as a negative electrode test for a sodium ion battery;
FIG. 9 is a graph showing the cycle performance of the ammonium borate modified carbon-based nanofiber materials prepared in comparative example 1 and examples 1 to 4 according to the present invention as a negative electrode test for 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 the ammonium borate modified carbon-based nanofiber materials prepared in example 1, example 7 and example 8 of the present invention;
Fig. 13 is a graph showing the cycle performance of the ammonium borate modified carbon-based nanofiber materials prepared in example 1, example 7 and example 8 according to the present invention as a negative electrode test of a sodium ion battery.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the 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 for purposes of illustration only and are not intended to limit the scope of 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;
carrying out electrostatic spinning on the precursor solution to obtain a nanofiber precursor film;
pre-oxidizing the nanofiber precursor film, specifically, pre-oxidizing in air;
immersing the pre-oxidized nanofiber precursor film in an ammonium borate solution, and then taking out the film for drying and carbonizing to obtain the ammonium borate modified carbon-based nanofiber composite material.
In the preparation method of the ammonium borate modified carbon-based nanofiber composite material, a carbon-containing high molecular polymer is used as a carbon source, and an ammonium borate solution impregnation doping mode is combined to obtain the ammonium borate modified carbon-based nanofiber material. The preparation method is simple to operate, environment-friendly, wide in sources of raw materials, low in cost and more suitable for wide production.
The ammonium borate modified carbon-based nanofiber material has a rich conductive network structure in the interior, and can effectively improve the electronic and ionic conductivity, so that the material can be used as a negative electrode material and also has the function of being used as a current collector in a battery component in sodium ion battery application. 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 can be reduced, and the overall energy density of the battery can be improved.
The carbon-based nanofiber is modified by doping boron and nitrogen in an ammonium borate solution impregnation mode, so that defect sites of the nanofiber are remarkably increased, the adsorption effect of the anode material on lithium/sodium ions is improved, the carbon layer spacing of the modified carbon-based nanofiber is enlarged, and the deintercalation-intercalation of lithium/sodium ions and the storage of the carbon material in the charge-discharge process are facilitated.
In some embodiments, the high molecular weight polymer is present in an amount of 6% to 12% by mass 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, 0.15mol/L.
In some embodiments, the high molecular 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.
In some embodiments, the process conditions of electrospinning include: the spinning voltage is 10-20kV, the receiving distance is 10-18cm, the propelling speed is 0.2-0.5mL/h, the spinning environment temperature is 20-40 ℃, and the 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 time ranging from 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: heating the dried nanofiber precursor film to 600-1000 ℃ at a heating rate of 1-5 ℃/min under a protective atmosphere, and preserving heat for 1-3h. Specifically, the protective atmosphere is nitrogen, argon or hydrogen.
On the other hand, the embodiment of the invention also provides an ammonium borate modified carbon-based nanofiber composite material, which is prepared by the preparation method of any one of the ammonium borate modified carbon-based nanofiber composite materials, wherein the microstructure 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 nanofiber.
On the other hand, the embodiment of the invention also provides the 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 invention is further illustrated by the following examples.
Example 1
The embodiment is used for illustrating a preparation method of the ammonium borate modified carbon-based nanofiber composite material, and comprises the following steps:
1) Dissolving polyacrylonitrile in an N, N-dimethylformamide solvent, and stirring with great force to prepare a transparent polymer precursor solution with the mass-volume ratio of 10%;
2) Preparing a polymer nanofiber film from the spinning solution 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 2 hours at 260 ℃ in an air atmosphere to obtain a pre-oxidized nanofiber membrane;
4) Immersing the pre-oxidized nanofiber membrane in an ammonium borate solution with the concentration of 0.02mol/L for 24 hours, and then taking out and drying at 60 ℃ for 8 hours to obtain an ammonium borate-impregnated nanofiber membrane with the concentration of 0.02 mol/L;
5) And (3) placing the obtained ammonium borate impregnated nanofiber film in a tubular furnace, and performing heat treatment for 1h at 600 ℃ in a protective atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the ammonium borate modified carbon-based nanofiber material.
Example 2
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that: the concentration of the ammonium borate solution was 0.05mol/L.
Example 3
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that: the concentration of the ammonium borate solution was 0.1mol/L.
Example 4
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that: the concentration of the ammonium borate solution was 0.15mol/L.
Example 5
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that: the mass fraction of polymer in the precursor solution was 8%.
Example 6
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that: the mass fraction of polymer in the precursor solution was 12%.
Example 7
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that:
the carbonization conditions are as follows: heat treatment at 800 deg.c for 1 hr.
Example 8
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 1, which are different in that:
The carbonization conditions are as follows: heat treatment at 1000 deg.c for 1 hr.
Example 9
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 2, which are different in 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 at 600 ℃ for 3 hours, and the heating rate is 3 ℃/min.
Example 10
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 3, which are different in that:
The pre-oxidation conditions were: pre-oxidizing for 3h at 240 ℃, wherein the concentration of the ammonium borate solution is 0.1mol/L, soaking the pre-oxidized nanofiber membrane in the ammonium borate solution for 36h, and then taking out and drying for 6h at 80 ℃;
the carbonization conditions are as follows: heat treatment is carried out at 600 ℃ for 2 hours, and the heating rate is 3 ℃/min.
Example 11
This example is for illustrating the preparation method of the ammonium borate modified carbon-based nanofiber composite disclosed in the present invention, and comprises most of the operation steps in example 4, which are different in that: the mass fraction of polymer in the precursor solution is 6%, and the pre-oxidation conditions are: pre-oxidizing for 1h at 280 ℃, wherein the concentration of the ammonium borate solution is 0.15mol/L, soaking the pre-oxidized nanofiber membrane in the ammonium borate solution for 30h, and then taking out and drying for 12h at 80 ℃;
The carbonization conditions are as follows: heat treatment is carried out at 600 ℃ for 1h, and the heating rate is 2 ℃/min.
Comparative example 1
This comparative example is a comparative illustration of the preparation of the ammonium borate modified carbon-based nanofiber composites disclosed herein, comprising a majority of the operating steps of example 1, with the differences: and (3) placing the pre-oxidized nanofiber membrane into a tube furnace, and performing heat treatment for 1h at 600 ℃ in a protective atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the carbon-based nanofiber material.
The beneficial effects of the invention are further illustrated by the test below.
Cutting the prepared carbon-based nanofiber membrane into a wafer with the diameter of 12mm, cleaning the wafer with alcohol, and then placing the wafer into a vacuum drying oven for vacuum drying at 70 ℃ for 24 hours, and then directly using the wafer as a self-supporting negative electrode. And placing the dried self-supporting anode material in a glove box, and assembling the 2032 button cell for subsequent electrochemical performance test. Wherein, the alternating current impedance test condition is 0.01Hz-100kHz, the cycle performance test condition is 100mA g -1, and the current density is between 0 and 3.0V for constant current charge and discharge test.
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 test of the embodiment 1-the embodiment 11, the ammonium borate modified carbon nanofiber prepared by the invention shows excellent specific discharge capacity and cycle stability as a self-supporting anode material for a sodium ion battery, and after 100 weeks of charge-discharge cycle, the reversible specific charge-discharge capacity of the battery can reach 315.6mAh/g, so that the self-supporting anode material has a wide application prospect.
Comparing the scanning electron micrographs of the obtained samples of comparative example 1 and examples 1 to 4 of fig. 1 to 5 together, it was found that the nanofiber surface was gradually roughened by the impregnation with ammonium borate, since NH 3 decomposed from the impregnated ammonium borate during the heat treatment had a pore-forming effect, thereby forming a porous structure and enhancing the surface activity of the material. When the fiber membrane is used as a self-supporting negative electrode of the battery, lithium/sodium ions can be adsorbed more effectively, so that the overall working efficiency and the service life of the battery are improved. However, as the impregnation concentration of ammonium borate increases, some micro cracks appear gradually on the surface of the 0.10mol/L ammonium borate modified carbon-based nanofiber membrane shown in FIG. 4, and larger-area breakage of carbon nanofibers appears on the surface of the 0.15mol/L ammonium borate modified carbon-based nanofiber membrane obtained in FIG. 5. Meanwhile, as the impregnation concentration of ammonium borate increases, the brittleness of each obtained ammonium borate modified carbon-based nanofiber film also increases macroscopically. The above results indicate that moderate impregnation of ammonium borate is advantageous for maintaining the toughness of the self-supporting anode material, and if excessive, it is likely to be disadvantageous for alleviating the volume expansion generated during the metal ion deintercalation process, and therefore, the concentration of ammonium borate is preferably 0.02 to 0.10mol/L.
FIG. 6 is an XRD pattern of the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1 to 4, and it is understood 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 when the impregnation concentration of ammonium borate was high (0.10 and 0.15 mol/L), a crystallization peak occurred at 28.1℃and the comparative PDF card was presumed to be due to the fact that the fiber film crystallized out of a certain B-containing crystal due to the excessive concentration of the ammonium borate solution. Meanwhile, as the impregnation concentration of ammonium borate increases, the carbon interlayer spacing of each sample was 0.390 (comparative example 1), 0.388 (example 1), 0.391 (example 2), and 0.393 (example 3), respectively, indicating that carbon nanofibers after impregnation of ammonium borate were doped with boron and nitrogen atoms, resulting in a reduction in the carbon interlayer spacing, but as the doping concentration increases, the interlayer spacing was instead greater than that of undoped fiber films.
FIG. 7 is a Raman diagram of the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1-3, from which it is seen that the Raman spectra of all samples show a D peak (1350 cm -1, indicating the defect level) and a G peak (1580 cm -1, indicating the graphitization level). As is evident from 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 0.02mol/L ammonium borate solution-impregnated carbon nanofiber membrane was relatively high.
Fig. 8 is a graph showing the ac impedance of the battery using the ammonium borate modified carbon-based nanofiber material prepared in comparative example 1 and examples 1 to 4 as a negative electrode test of a sodium ion battery, and as can be seen from the graph and table 1, the resistance values of the sodium ion battery assembled by using the carbon-based nanofiber self-supporting negative electrodes prepared in comparative example 1 and examples 1 to 4 in the intermediate frequency region are respectively: 501.2, 299.4, 378.7, 146.5 and 200.4. Compared to the sample not modified with ammonium borate, the following advantages are obtained: (1) The carbon-based material is doped and modified by B, N atoms through modifying the carbon-based nanofiber by ammonium borate, so that the electron and ion conduction capacity of the self-supporting anode of the carbon-based nanofiber is improved; (2) As the impregnation concentration of ammonium borate increases, the impedance of the battery formed by the self-supporting negative electrode of the modified carbon-based nanofiber tends to decrease, and the raman characterization result (shown in fig. 7) analysis of the binding material shows that the conductivity of the carbon material is enhanced by introducing more B, N atoms.
Fig. 9 is a graph showing the cycle performance of the ammonium borate modified carbon-based nanofiber materials prepared in comparative example 1 and examples 1 to 4 as a negative electrode test for sodium ion batteries, which was performed at a current density of 100mA g -1. As can be seen from fig. 9 in combination with table 1, compared with the carbon nanofiber membrane anode prepared in comparative example 1, the modification of ammonium borate (0.02 mol/L ammonium borate impregnation) with moderate concentration can introduce more abundant defect sites into the carbon-based self-supporting anode material, thereby enhancing the adsorption of sodium ions by the anode and facilitating the intercalation and deintercalation of sodium ions, and meanwhile, the appropriate layer spacing of the carbon material may also contribute to forming more abundant closed cell structures, thereby improving the storage of sodium ions, and improving the initial capacity and the cycle stability of the battery to a greater extent. Along with the increase of the ammonium borate concentration, the B, N atom doping content is further increased, the introduced defects are greatly reduced, and meanwhile, the expansion of the interlayer spacing probably causes the defect of closed pores, so that the initial discharge capacity of the sodium ion battery formed by the sodium ion battery is reduced.
Fig. 12 is XRD patterns of samples of examples 1, 7 and 8 prepared using different heat treatment temperatures, from which it is understood that all samples have only typical carbon peaks, and from fig. 1, 10 and 11, the carbon layer spacing of the ammonium borate modified carbon-based nanofiber materials of examples 1, 7 and 8 are 0.388, 0.386 and 0.383nm, respectively, indicating that the material layer spacing decreases as the heat treatment temperature increases.
Fig. 13 is a graph showing the cycle performance of the ammonium borate modified carbon-based nanofiber materials prepared in examples 1, 7 and 8 as a negative electrode test for sodium ion batteries, which was performed at a current density of 100mA g -1. As can be seen from the graph, all samples have good cycle stability, but as the heat treatment temperature increases during sample preparation, the initial discharge capacity of the battery shows a tendency to gradually decrease, probably due to the decrease in carbon interlayer spacing caused by the increase in temperature, and thus the pore structure is unfavorable for intercalation of metal ions. It can thus be seen that the heat treatment temperature for carbonization is preferably 600-800 ℃.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
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;
carrying out electrostatic spinning on the precursor solution to obtain a nanofiber precursor film;
pre-oxidizing the nanofiber precursor film, wherein the pre-oxidation temperature is 220-280 ℃ and the pre-oxidation time is 1-4 hours;
Immersing the pre-oxidized nanofiber precursor film in an ammonium borate solution for 20-36h, wherein the concentration of the ammonium borate solution is 0.02-0.15mol/L; and then taking out the carbon-based nano fiber composite material to be dried and carbonized to obtain the ammonium borate modified carbon-based nano fiber composite material, wherein the carbonization treatment process comprises the following steps: heating the dried nanofiber precursor film to 600-1000 ℃ at a heating rate of 1-5 ℃/min under a protective atmosphere, and preserving heat for 1-3h.
2. The method for producing an ammonium borate modified carbon-based nanofiber composite 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 for preparing an ammonium borate modified carbon-based nanofiber composite according to claim 1, wherein the high molecular 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.
4. The method for preparing an ammonium borate modified carbon-based nanofiber composite according to claim 1, wherein the process conditions of the electrospinning comprise: the spinning voltage is 10-20kV, the receiving distance is 10-18cm, the propelling speed is 0.2-0.5mL/h, the spinning temperature is 20-40 ℃, and the environmental humidity is 15-60RH%.
5. The method for preparing an ammonium borate modified carbon-based nanofiber composite according to claim 1, wherein the drying conditions are as follows: the drying temperature is 50-80 ℃ and the drying time is 6-12h.
6. An ammonium borate modified carbon-based nanofiber composite material, which 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 1-5, wherein the microstructure of the ammonium borate modified carbon-based nanofiber composite material is of a three-dimensional cross-linked network structure, and boron and nitrogen are co-doped in carbon-based nanofibers.
7. The use of the ammonium borate modified carbon-based nanofiber composite of claim 6 in a battery negative electrode or in a fast charge lithium/sodium ion battery.
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