CN112279304A - Fe3O4Porous carbon nanofiber and preparation method and application thereof - Google Patents
Fe3O4Porous carbon nanofiber and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002134 carbon nanofiber Substances 0.000 title description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 15
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000010902 straw Substances 0.000 claims abstract description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000002133 porous carbon nanofiber Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 238000000034 method Methods 0.000 claims description 21
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- QZELMXYYONEIDT-UHFFFAOYSA-N 3,3-diacetylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)(C(C)=O)C(C)=O QZELMXYYONEIDT-UHFFFAOYSA-N 0.000 claims description 6
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 abstract description 10
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 3
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
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- 229910000859 α-Fe Inorganic materials 0.000 description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000001721 carbon Chemical group 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses Fe3O4Porous carbon nanofiber and a preparation method and application thereof, relating to the technical field of electrode materials and preparation methods thereof, wherein the preparation method comprises the following steps: mixing the straw liquefied carbon, polyacrylonitrile, ferric triacetylacetonate and alpha-cyclodextrin to obtain a mixture, and dissolving the mixture in N, N-dimethylObtaining an electrostatic spinning solution in formamide; carrying out electrostatic spinning on the electrostatic spinning solution to prepare a composite nanofiber membrane; drying the prepared composite nanofiber membrane to remove N, N-dimethylformamide, soaking in an alpha-amylase aqueous solution, sealing, heating and hydrolyzing at 70 ℃ for 90min, taking out, and washing ferric triacetylacetonate and hydrolysate which fall off from the surface; and (4) carrying out freeze drying and carbonization treatment on the washed composite nanofiber membrane. The nano-fiber material prepared by the invention is 1 A.g‑1Has a specific capacitance of 163.1 F.g‑1At 10A · g‑1Can be maintained at 127F g‑1。
Description
Technical Field
The invention relates to the technical field of electrode materials and preparation methods thereof, in particular to Fe3O4Porous carbon nanofiber and preparation method and application thereof.
Background
The super capacitor is a novel energy storage device, has the advantages of rapid charging, rapid discharging, excellent cycling stability, high power density and the like, and the proper electrode material is the key point for developing the high-performance super capacitor.
Whether the carbon material is applied to an electric double layer capacitor or the carbon skeleton material of a pseudo-capacitance capacitor, the activation process is a key step for preparing the biomass carbon material. In the process, the pore structure of the biomass carbon material is formed, the specific surface area is increased, the electrolyte can be favorably infiltrated into the surface of the electrode, the open pores can provide more charge storage places and transmission channels, the diffusion distance of ions is shortened, the activation on the improvement of the electrochemical performance is an effective method for generating pores and expanding the existing pores or modifying the pores.
Two types of activation are currently in common use: namely physical activation and chemical activation. Physical activation utilizes carbon dioxide, steam or a mixture of these gases to create porosity. These species react with carbon atoms to form carbon monoxide, resulting in a structural change. The obtained width of the micro-pores has relatively loose correlation with experimental parameters such as temperature, pressure, heating rate and the like. In the chemical activation process, the action between activating agents such as potassium hydroxide, zinc chloride or phosphoric acid and carbon occurs at a certain temperature, the raw materials are dehydrated or eroded, the chemical activation can better control the pore size distribution and obtain a higher specific surface area and a higher yield than the physical activation, meanwhile, functional groups on the surface of the material are increased, the wettability of the material to electrolyte is improved, the diffusion resistance of an electrode and the electrolyte is reduced, and the electrochemical performance of the carbon material is improved. However, chemical activation has certain corrosion characteristics, requires strict cleaning, and more importantly, the yield of the carbon material after the activation treatment is reduced, and the electrochemical performance of the material is also affected.
Disclosure of Invention
In order to solve the above problems, the present invention provides Fe3O4Porous carbon nanofiber and preparation method and application thereof, wherein enzymatic hydrolysis of alpha-cyclodextrin by medium-temperature alpha-amylase is used as a pore-enlarging method, ferric acetylacetonate is used as an iron oxide precursor, hemp straw is converted into liquefied carbon and doped into electrostatic spinning precursor liquid to prepare Fe with excellent structure and electrochemical performance3O4Porous carbon nanofiber materials.
In order to achieve the purpose, one of the technical schemes adopted by the invention is as follows: fe3O4A preparation method of porous carbon nanofiber comprises the following steps:
s1: mixing straw liquefied carbon, polyacrylonitrile, ferric triacetylacetone and alpha-cyclodextrin to obtain a mixture, and dissolving the mixture in N, N-dimethylformamide to obtain an electrostatic spinning solution;
s2: carrying out electrostatic spinning on the electrostatic spinning solution to prepare a composite nanofiber membrane;
s3: drying the prepared composite nanofiber membrane to remove N, N-dimethylformamide, soaking in an alpha-amylase aqueous solution for sealing, heating and hydrolyzing at 70 ℃ for 90min, taking out, and washing ferric triacetylacetonate and hydrolysate which fall off from the surface;
s4: carrying out freeze drying and carbonization treatment on the washed composite nanofiber membrane to obtain Fe3O4Porous carbon nanofiber materials.
Further, the straws are hemp straws, corn straws, wheat straws, rice straws,
One kind of rape stalk.
Furthermore, the mass ratio of the straw liquefied carbon to the polyacrylonitrile is 1: 9.
Further, the straw liquefied carbon is mixed with the polyacrylonitrile to form LC-PAN.
Further, the mass ratio of the LC-PAN to the alpha-cyclodextrin is 7: 3.
Further, the mass of the ferric triacetylacetone accounts for 3% of the mass of the mixture.
Furthermore, the mass ratio of the medium-temperature alpha-amylase to the alpha-cyclodextrin is 5: 1.
Further, the carbonization treatment is: pre-oxidizing the freeze-dried composite nanofiber membrane in a muffle furnace at 260 ℃ for 1h in air at the heating rate of 1 ℃ min-1Subsequently at N2At 2 ℃ min under protection-1The temperature rising rate is increased to 900 ℃, the carbonization is carried out for 1 hour at constant temperature, and the natural cooling is carried out.
The second technical scheme of the invention is as follows: fe prepared by the method of any one of the above technical schemes3O4Porous carbon nanofibers.
The third technical scheme of the invention is as follows: fe according to the technical scheme3O4Application of porous carbon nanofiber material as capacitor electrode material.
The invention has the beneficial effects that:
fe prepared by the invention3O4The porous carbon nanofiber material takes iron acetylacetonate as an iron-based compound precursor, liquefied carbon prepared from plant straws is mixed in electrostatic spinning precursor liquid for electrostatic spinning to prepare a composite material taking carbon nanofibers as a carbon skeleton, and the prepared carbon nanofiber carbon skeleton is subjected to reaming activation in a mode of carrying out enzyme hydrolysis on alpha-cyclodextrin by using medium-temperature alpha-amylase to obtain biological micromolecules such as maltose, glucose and the like, so that Fe with excellent structure and electrochemical performance is prepared3O4Porous carbon nanofiber materials;
fe by SEM and BET3O4The observation of the morphology and structure of the porous carbon nanofiber material shows that the enzymatic hydrolysis reaction of the medium-temperature alpha-amylase on the alpha-cyclodextrin has a positive effect on the generation of pores in the carbon nanofiber, so that the nanofiberThe specific surface area of the film is changed from original 26.37 m2·g-1Increased to 268.09 m2·g-1。
TEM, XRD, Raman and XPS characterization is adopted to prove that ferric acetylacetonate is converted into Fe through the pre-oxidation and carbonization processes3O4The carbon nano-fiber is stably and uniformly loaded in a carbon skeleton of the carbon nano-fiber to realize the electrochemical function of the pseudo-capacitor.
Electrochemical performance measurements in a three-electrode system showed: the composite electrode material after pore expansion through medium-temperature alpha-amylase activation has better electrochemical performance at 1 A.g-1The specific capacitance below is 1.3 times that of the unactivated pore-expanding composite and exhibits excellent rate capability and less electrochemical impedance capability.
The materials after enzyme activation are assembled into a symmetrical super capacitor device at 1 A.g-1Has a specific capacitance of 163.1 F.g-1At 10A · g-1Can be maintained at 127F g-1The specific capacitance of the capacitor reaches 213F g when the current density is 0.5A g-1-1And the capacity retention rate can reach 94.31 percent and is from 1 A.g-1Change to 10A g-1The specific capacity retention rate is as high as 77.9%, which indicates that the Fe of the invention is adopted3O4The capacitor prepared from the porous carbon nanofiber material maintains excellent stability throughout the charge and discharge tests.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 shows FePCNF according to an embodiment of the present invention1SEM images before and after carbonization, wherein a-c are FePCNF1SEM pictures of different magnifications before pre-oxidation; d-f is FePCNF1SEM pictures of different magnifications after carbonization;
FIG. 2 shows FePCNF according to an embodiment of the present invention1Wherein a is a TEM image, b is an HRTEM image, and c is a SAED image;
FIG. 3 shows FePCNF according to an embodiment of the present invention0And FePCNF1N2 adsorption-desorption isotherm;
FIG. 4 is FePCNF of an embodiment of the invention0And FePCNF1Pore size distribution curve of (a);
FIG. 5 is FePCNF of an embodiment of the invention0And FePCNF1XRD spectrum of (1);
FIG. 6 is FePCNF of an embodiment of the invention0And FePCNF1Raman spectrum of (a);
FIG. 7 is FePCNF of an embodiment of the invention1Wherein a is an XPS spectrogram, b is a C1 s high-resolution spectrogram, C is an O1 s high-resolution spectrogram, and d is an Fe 2p high-resolution spectrogram;
FIG. 8 shows FePCNF in a three-electrode system according to an embodiment of the present invention0And FePCNF1Wherein a is FePCNF0And FePCNF1At 10 mV · s-1CV curve at the scan rate of (a); b is FePCNF1At 5 to 50mV · s-1CV curve at the scan rate of (a); c is at a current density of 1 A.g-1FePCNF0And FePCNF1A GCD curve of (1); d is FePCNF under different current densities1A GCD curve of (1);
FIG. 9 shows FePCNF in a three-electrode system according to an embodiment of the present invention0And FePCNF1Specific capacitance at different current densities;
FIG. 10 shows FePCNF in a three-electrode system in accordance with an embodiment of the present invention0And FePCNF1The alternating current impedance of (1);
FIG. 11 shows FePCNF in an example of the present invention1//FePCNF1Symmetrical capacitors in the range of 5 to 100 mV. s-1CV curve at scan rate;
FIG. 12 is FePCNF of an embodiment of the invention1//FePCNF1The GCD curve of the symmetrical capacitor under different current densities;
FIG. 13 shows FePCNF in accordance with an embodiment of the present invention1//FePCNF1The specific capacitance of the symmetrical capacitor is different under different current densities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides Fe3O4A preparation method of porous carbon nanofiber comprises the following steps:
s1: mixing straw liquefied carbon, polyacrylonitrile, ferric triacetylacetone and alpha-cyclodextrin to obtain a mixture, and dissolving the mixture in N, N-dimethylformamide to obtain an electrostatic spinning solution;
s2: carrying out electrostatic spinning on the electrostatic spinning solution to prepare a composite nanofiber membrane;
s3: drying the prepared composite nanofiber membrane to remove N, N-dimethylformamide, soaking in an alpha-amylase aqueous solution for sealing, heating and hydrolyzing at 70 ℃ for 90min, taking out, and washing ferric triacetylacetonate and hydrolysate which fall off from the surface;
s4: carrying out freeze drying and carbonization treatment on the washed composite nanofiber membrane to obtain Fe3O4Porous carbon nanofiber materials.
In the embodiment of the application, the composite nanofiber membrane is prepared by using an electrostatic spinning technology, and the specific parameters are as follows: adding the electrostatic spinning solution into a 5 mL plastic syringe with a stainless steel needle (24-gauge needle); the negative high voltage is-2 kV, and the positive high voltage is 13 kV; the distance between the collector (aluminum foil) and the nozzle was fixed at 15 cm; the flow rate was 0.14 mm min-1(ii) a The ambient temperature was 23 ℃. In the embodiment of the application, N-Dimethylformamide (DMF) is used as a solvent, so that the solubility is good. In the embodiment of the application, alpha-amylase with the enzyme activity of 4000 u g is adopted-1. In the enzymatic hydrolysis process, a moderate temperature alpha-amylase, i.e., 1, 4-alpha-D-glucan hydrolase, extracted from Bacillus subtilis,at the temperature: 70 ℃, pH value: 5-7, the alpha-amylase can hydrolyze alpha-1, 4-glycosidic bonds in the cyclodextrin. The reaction is generally carried out in two stages: firstly, alpha-amylase can hydrolyze alpha-1, 4-glycosidic bonds in cyclodextrin to rapidly degrade the cyclodextrin to generate oligosaccharide; the second stage oligosaccharides are slowly hydrolyzed to yield the final products glucose and maltose. These small molecular substances fall off from their original positions and form pores in the carbon skeleton.
In some embodiments, Fe3O4The preparation method of the porous carbon nanofiber further comprises the following steps of: weighing a certain amount of hemp straws, washing the hemp straws with deionized water, drying the hemp straws in an oven at 80 ℃ for 8 hours, crushing the dried straws, sieving the crushed straws with a 100-mesh sieve, adding phenol which is 5 times of the weight of the straw powder and phosphoric acid which is 10% of the weight of the straw powder, wherein the phosphoric acid is used as a catalyst, carrying out oil bath reflux at 160 ℃ for 2.5 hours, and cooling to room temperature to obtain the straw liquefied carbon.
Fe prepared by the invention3O4Porous carbon nanofiber material, which is characterized in that ferric triacetylacetonate is used as an iron-based compound precursor, liquefied carbon prepared from plant straws is used as a carbon skeleton, electrostatic spinning is carried out to prepare a composite material with carbon nanofibers as the carbon skeleton, and pore-expanding activation is carried out on the prepared carbon nanofiber carbon skeleton in a mode that middle-temperature alpha-amylase carries out enzymatic hydrolysis on alpha-cyclodextrin to obtain biological micromolecules such as maltose, glucose and the like, so that Fe with excellent structure and electrochemical performance is prepared3O4Porous carbon nanofiber materials.
Further, the straws are hemp straws, corn straws, wheat straws, rice straws,
One kind of rape stalk.
Fe prepared by the invention3O4The liquefied carbon prepared from the straws is used as the carbon skeleton, so that the porous carbon nanofiber material is green and environment-friendly, and the production cost is saved.
Furthermore, the mass ratio of the straw liquefied carbon to the polyacrylonitrile is 1: 9.
Further, the straw liquefied carbon is mixed with the polyacrylonitrile to form LC-PAN.
Further, the mass ratio of the LC-PAN to the alpha-cyclodextrin is 7: 3.
Further, the mass of the ferric triacetylacetone accounts for 3% of the mass of the mixture.
Furthermore, the mass ratio of the medium-temperature alpha-amylase to the alpha-cyclodextrin is 5: 1.
Further, the freeze-drying is carried out at-10 ℃.
In the embodiment of the application, the cleaned composite nanofiber membrane is placed in a freeze dryer for freeze drying at-10 ℃ to prevent the change of the pore structure.
Further, the carbonization treatment is: pre-oxidizing the freeze-dried fiber membrane in a muffle furnace at 260 ℃ for 1h in air at the heating rate of 1 ℃ min-1Subsequently at N2At 2 ℃ min under protection-1The temperature rising rate is increased to 900 ℃, the carbonization is carried out for 1 hour at constant temperature, and the natural cooling is carried out.
In the examples of the present application, after the carbonization treatment, Fe having a porous structure was obtained3O4Porous carbon nanofiber materials.
The invention also provides Fe3O4Application of porous carbon nanofiber material as capacitor electrode material.
Example 1
The embodiment of the invention provides Fe3O4A preparation method of porous carbon nanofiber comprises the following steps:
mixing 0.7g of hemp straw liquefied carbon, 6.3g of polyacrylonitrile, 9g of alpha-cyclodextrin and 0.48g of ferric triacetylacetonate; dissolving the mixture in N, N-Dimethylformamide (DMF), and stirring until the mixture is completely dissolved to obtain an electrostatic spinning solution;
the composite nanofiber membrane is prepared by utilizing an electrostatic spinning technology, and the specific parameters are as follows: adding the electrostatic spinning solution into a 5 mL plastic syringe with a stainless steel needle (24-gauge needle); the negative high voltage is-2 kV, and the positive high voltage is 13 kV; the distance between the collector (aluminum foil) and the nozzle was fixed at 15 cm; the flow rate was 0.14 mm min-1(ii) a The ambient temperature was 23 ℃.
Adding 45g of medium-temperature alpha-amylase into 200mL of deionized water in a 250 mL beaker for dissolving to obtain a medium-temperature alpha-amylase solution, and uniformly stirring and dispersing for later use; putting the prepared composite nanofiber membrane into an oven, drying at 60 ℃ to remove N, N-dimethylformamide, soaking in uniformly dispersed medium-temperature alpha-amylase solution, sealing, heating and hydrolyzing at 70 ℃ for 90min, taking out, and washing ferric triacetylacetonate and hydrolysate which fall off from the surface until the washing solution is completely free of impurities; then freeze-drying at-10 deg.C.
Pre-oxidizing the freeze-dried composite nanofiber membrane in air at 260 ℃ in a muffle furnace for 1h at the heating rate of 1 ℃ min-1, raising the temperature to 900 ℃ at the heating rate of 2 ℃ min-1 under the protection of N2, carbonizing for 1h at the constant temperature, and naturally cooling to obtain the enzyme-expanded iron-based porous carbon nanofiber composite material which is marked as FePCNF 1.
Comparative example 1
Fe3O4A preparation method of porous carbon nanofiber comprises the following steps:
mixing 0.7g of hemp straw liquefied carbon, 6.3g of polyacrylonitrile, 9g of alpha-cyclodextrin and 0.48g of ferric triacetylacetonate; dissolving the mixture in N, N-Dimethylformamide (DMF), and stirring until the mixture is completely dissolved to obtain an electrostatic spinning solution;
the composite nanofiber membrane is prepared by utilizing an electrostatic spinning technology, and the specific parameters are as follows: adding the electrostatic spinning solution into a 5 mL plastic syringe with a stainless steel needle (24-gauge needle); the negative high voltage is-2 kV, and the positive high voltage is 13 kV; the distance between the collector (aluminum foil) and the nozzle was fixed at 15 cm; the flow rate was 0.14 mm min-1(ii) a The ambient temperature was 23 ℃.
Putting the prepared composite nanofiber membrane into an oven, drying at 60 ℃ to remove N, N-dimethylformamide, and washing the ferric triacetylacetonate dropped off from the surface until the washing solution is completely free of impurities; then freeze-drying at-10 deg.C.
Pre-oxidizing the freeze-dried composite nanofiber membrane in a muffle furnace at 260 ℃ for 1h in air at the heating rate of 1Min-1, then raising the temperature to 900 ℃ at the heating rate of 2 ℃ min-1 under the protection of N2, carbonizing for 1h at the constant temperature, and naturally cooling to obtain the enzyme-expanded iron-based porous carbon nanofiber composite material marked as FePCNF0。
Examples of the experiments
(I) morphology and Structure characterization
FIG. 1 shows FePCNF prepared in example 11Scanning Electron Microscope (SEM) characterization comparison is carried out on a sample before enzyme activation (namely a nanofiber membrane obtained by electrostatic spinning) and a sample after carbonization, and in SEM images with different magnifications, the obtained carbon nanofiber has uniform diameter distribution, smooth and clean surface and no obvious protrusion or protruding part before enzyme activation as shown in a-c in figure 1. After being subjected to enzymatic hydrolysis, pre-oxidation and carbonization, as shown in d-f in fig. 1, it can be seen that the one-dimensional structure of the fibers is maintained and continuous, the fibers are independent from each other, no adhesion phenomenon occurs between the fibers, the surface of the fibers is rough, and a plurality of small protrusions are present on the surface, and the rough small protrusions are caused by pores, and the structure is favorable for increasing the specific surface area of the carbon nanofiber. It can thus be seen that: the enzyme activation method adopted by the invention generates a certain pore structure and increases the specific surface area of the material, which plays a positive role in the conduction of electrons and ions in the electrochemical process.
To further confirm FePCNF1Structural characteristics of (1) and the compounding condition of the (B) and iron oxide compound, for the material FePCNF1Image characterization by Transmission Electron Microscopy (TEM) was performed. FePCNF as shown in a in FIG. 21The rough surface of the material indicates significant porosity with nanoparticles uniformly embedded in the carbon nanofiber material. For FePCNF1The selected area is characterized by a high-resolution transmission electron microscope (HRTEM), as shown in a b in figure 2, bright-dark staggered and ordered lattice stripes can be seen on the surface of the material after cleaning, and the interplanar spacing is calculated to be 0.25nm and corresponds to cubic phase Fe3O4The iron oxide compound obtained by the method is Fe3O4And with carbon nano-meterThe fiber has better combination property.
The SAED pattern of selected regions c in fig. 2 shows regular diffraction rings further showing the Fe formed3O4Is highly crystalline.
To further analyze the superiority of the biological enzyme activation method, FePCNF prepared in comparative example 1 was used0And FePCNF prepared in example 11N of material measurement2The adsorption-desorption isotherms and pore size distributions were subjected to correlated pore structure characterization, and the data obtained are shown in fig. 3. FIG. 3 is N of the material2Adsorption-desorption isotherms, FePCNF, according to the International Union of Pure and Applied Chemistry (IUPAC) classification0And FePCNF1The absorption-desorption curves are shown as IV-type absorption isotherms, which shows that the material has uniform micropore and mesoporous structures. At P/P0Within the range of 0.2-1.0, significant desorption curve hysteresis appears, indicating the presence of mesopores in both materials. Because the carbon nanofibers are doped with the ferrite compounds, certain pores can be generated due to the existence of the ferrite compounds, and a certain pore structure can be generated after the carbon nanofibers are activated by enzyme, the mesopores are the result of the joint generation of the pores caused by the existence of the ferrite compounds and the activation of the enzyme through preliminary analysis. At a relative pressure P/P0Is in the range of 0.9-1.0N2The adsorption quantity is obviously increased, which indicates that a certain macroporous structure also exists in the material. Therefore, micropores, mesopores and macropores are uniformly distributed in the structure. In these pore structures, the macropores provide an electrolyte reservoir to reduce the distance between the interface and the inner surface, the mesopores provide stable channels for ion migration, and the micropores are electrically conductive to further increase the specific capacitance of the supercapacitor. The pore size distribution curves of the samples calculated by using the Barrett-Joyner-Halenda (BJH) method are shown in FIG. 4, where FePCNF can be seen0And FePCNF1The material has a continuous pore size distribution.
From N2The adsorption curve is calculated by a Brunauer-Emmett-Teller (BET) method to obtain FePCNF0And FePCNF1Detailed pore size distribution data are shown inTable 1. FePCNF0Has a specific surface area of 306.31 m2 g-1Total pore volume of 0.59m3·g-1The average pore diameter was 7.75 nm. FePCNF1Has a specific surface area of 412.96m2·g-1Total pore volume of 0.55m 3g-1The average pore diameter was 5.36 nm. With FePCNF0In contrast, FePCNF1The specific surface area of the porous material is slightly increased, and the average pore diameter is slightly reduced, which shows that the biological enzyme activation generates certain pores and increases certain specific surface area for the material. Therefore, the enzyme activation method has a certain positive effect on the improvement of the material pore structure, and the material with a larger specific surface area and an effective pore structure provides more surface interfaces for the material, promotes the migration of electrolyte, and thus improves the electrochemical performance of the material.
TABLE 1 FePCNF0And FePCNF1Pore performance parameter of
As shown in FIG. 5, for FePCNF0And FePCNF1The structure is subjected to XRD characterization and analysis, and FePCNF can be seen firstly0And FePCNF1A broad amorphous carbon diffraction peak occurs between 15 ° and 30 ° 2 θ, respectively, and the peaks occurring thereafter correspond to the (220), (311), (400), (331), (422), (440) and (620) crystal planes, respectively, with the (331) crystal plane diffraction peak being the highest and the (400) crystal plane diffraction peak being the second order, with the result being similar to Fe3O4The PDF cards (JCPDS card numbers 3-863) are in good agreement, and impurity peaks of other phases are not detected. Further indicates that the iron oxide compound synthesized by the method is Fe3O4And has high purity and good crystallinity.
To further determine the structural composition of the sample, FePCNF was examined0And FePCNF1The structure was subjected to Raman analysis, and as shown in FIG. 6, the results were first obtained at 1329cm each-1And 1592cm-1Shows stronger Raman absorption peaks corresponding to a D peak and a G peak in the carbon material respectively. Wherein the peak D is a lattice of carbon atomsDefect vibration causes, G peak is carbon atom sp2Hybrid in-plane stretching vibration. FePCNF0And FePCNF1The intensity ratios of the D peak to the G peak, i.e., ID/IG, of 1.18 and 1.19, respectively, indicate that the carbonized carbon material had many lattice defects on the surface. In contrast to the literature, for a band at 219cm-1And 290cm-1The two Raman absorption peaks shown are attributed to Fe3O4Wherein the absorption peak is 219cm-1Has an absorption peak of Fe3O4T of2gA vibration mode; 290cm-1Has an absorption peak of Fe3O4Eg vibration mode of (1). The Raman test results also prove that the iron-based compound formed is Fe3O4The form of nanoparticles is present in the carbon nanofibers.
XPS is considered to be one of the most accurate means for detecting the chemical bonding state of elements in a material, and the chemical combination state of the elements in the material can influence the electrochemical performance of the material. In order to explore FePCNF1C, O and the valence state of Fe element, which is characterized by XPS. The XPS signals for the elements C1 s, O1 s and Fe 2p are clearly seen from a in FIG. 7, illustrating FePCNF1The sample contains the above three elements. In FIG. 7, b shows three C1 s peaks mainly, which are located near 284.3, 285.1 and 286.4 eV corresponding to C-C sp2，C-C sp3And a C-O bond. The spectrum for O1 s is shown in FIG. 7 c, and includes three oxygen-containing functional groups, namely, an Fe-O having a binding energy of 530.16 eV, an Fe-O-H having a binding energy of 531.78 eV, and an oxygen-bonding functional group having a binding energy of H-O-H having a binding energy of 533.26 eV. D in FIG. 7 demonstrates that the element Fe is Fe3O4Exist in the form of (1), respectively corresponding to Fe 2p3/2And Fe 2p1/2The horizontal binding energies are around 711.86 and 725.25 eV. These results further indicate that the material formed is Fe3O4Carbon nanofiber composites, consistent with the analysis of the results of XRD, Raman spectroscopy and TEM characterization.
(II) characterization of electrochemical Properties of the Material
The effective contact area between the electrode material and the electrolyte is the main factor determining the electrochemical performance of the supercapacitorOne, the first step. When the conventional carbon nanofiber is used as a carbon skeleton of a pseudo-capacitor electrode material, the contact area between the electrode material and an electrolyte is limited to the surface of the material, and ions and electrons cannot diffuse into the electrode material, so that the utilization rate of the carbon skeleton material is low. Therefore, the method generates rich pores in the carbon skeleton material by the method of activating the biological enzyme, increases the specific surface area of the material, greatly increases the effective contact between the material and the electrolyte, increases the transmission performance of ions and electrons, and improves the electrochemical performance of the material. In order to verify whether the electrochemical performance of the iron-based composite material is effectively improved by the material after enzyme activation, FePCNF is subjected to reaction under a three-electrode system0And FePCNF1The electrode material was tested for electrochemical performance. The measurement environment is as follows: respectively with FePCNF0And FePCNF1Preparing a working electrode from an electrode material, taking a Pt sheet electrode as a counter electrode and an Hg/HgO electrode as a reference electrode, and measuring the concentration of the Pt sheet electrode and the Hg/HgO electrode at 6 mol.L-1The three-electrode test system formed in the KOH electrolyte is subjected to Cyclic Voltammetry (CV), constant current charging and discharging (GCD), Electrochemical Impedance Spectroscopy (EIS) and cyclic life tests, and the test results are shown in FIG. 8.
In FIG. 8, a is FePCNF0And FePCNF1The scanning speed of the material electrode is 10 mV.s-1When the pseudo-capacitance is measured, the Cyclic Voltammetry (CV) curve in the potential range of-1.2V to-0.4V can be seen to obviously deviate from a rectangular shape and have obvious oxidation and reduction peaks, so that the curve shows typical pseudo-capacitance behaviors, and the pseudo-capacitance behaviors can be analyzed to be measured by Fe3O4Contribution of compounds, and FePCNF1The CV curve area of the electrode is obviously larger than that of FePCNF0The CV curve area of (a) indicates that the electrode material has higher specific capacitance after pore expansion through enzyme activation. For FePCNF1Material, as can be seen from FIG. 8b, the scan rate is from 5 mV. multidot.s over the potential range of-1.2V to-0.4V-1Increase to 50mV · s-1The shape of the CV curve of the catalyst is not obviously changed, and the catalyst still maintains obvious oxidation and reduction peaks, which indicates that FePCNF1Has good electrochemical stability.
The same rule is embodied in constant current chargingIn the discharge (GCD) test results, FIG. 8c shows FePCNF0And FePCNF1Material electrode at 1A g-1And a potential range of-1.0V to-0.3V, both exhibit an asymmetric shape, and deviations from the linear GCD curve further confirm the presence of pseudocapacitive behavior. At the same time, it can be seen that FePCNF is present at the same current density1FePCNF0Exhibits a longer discharge time according to
The calculation can show that for FePCNF0And FePCNF1Have specific capacitances of 410 and 547F g, respectively-1，FePCNF1The specific capacitance of (C) is FePCNF01.3 times the specific capacitance. Further demonstrating that FePCNF was produced after enzyme activation1The electrode material has larger specific capacitance, so the effective contact area of the electrode material and an electrolyte is a main factor influencing the electrochemical performance of the electrode material, and an enzyme activation method is a feasible effective method for increasing the specific surface area and the porosity. (1, 2, 3, 5, 7 and 10 A.g) at different current densities-1）FePCNF1The GCD curve of (1) is shown in FIG. 8d at 1A · g-1When the temperature reaches 547F g-1At 10A · g-1Also maintained at 314 F.g at a high current density-1Therefore, the material can be suitable for occasions with different current density requirements.
The graph of the change in capacitance values in FIG. 9 was obtained from the GCD curves at different current densities, and it can be seen that the value is 1 A.g-1At current density of FePCNF0And FePCNF1Respectively show the maximum specific capacitance, and FePCNF is increased along with the increase of current density0And FePCNF1Gradually decreases in specific capacitance, but FePCNF1The slow down trend of the specific capacitance is obviously lower than the change of the specific capacitance of FePCNF0, which shows that the FePCNF1The excellent rate performance of the electrode material further indicates that the composite material after enzyme activation has more excellent electrochemical performance than the traditional material.
In order to further analyze the influence of the enzyme activation method on the electrochemical performance of the composite material, the obtained Fe is subjected toPCNF0And FePCNF1The electrode material is subjected to an alternating current impedance test, and an electrochemical alternating current impedance test chart comprises a semicircular curve in a high-frequency region, wherein the radius of the semicircular curve is related to a charge transfer resistance (Rct) and corresponds to the charge transfer resistance generated by an interface when the material is in contact with an electrolyte; an inclined curve of the low-frequency region is related to the diffusion resistance of ions embedded into pores of the electrode material, and the closer the curve is to the vertical axis, the stronger the capacitance characteristic is; the first intersection of the ac impedance curve with the abscissa is the equivalent series resistance (Rs), which is mainly determined by the electrode resistance, the electrolyte resistance and the interface resistance of the electrode and the electrolyte. As shown in FIG. 10, it can be seen that FePCNF0And FePCNF1With curves having almost the same slope in the low frequency region, the semi-circular radius of the FePCNF0 electrode was small compared to the FePCNF1 electrode, indicating that the FePCNF1 electrode has a smaller internal resistance. Calculating FePCNF0And FePCNF1The internal resistances (Rs) of the electrode materials are 1.09 and 0.76 omega respectively, and the same FePCNF1Has a small equivalent series resistance. Therefore, electrochemical alternating current impedance test analysis shows that the composite material FePCNF after enzyme activation1More active contact area is provided between the electrolyte and the electrolyte, and the diffusion of the electrolyte has smaller resistance.
FePCNF after enzyme activation in three-electrode system1The material shows excellent electrochemical performance, and in order to explore FePCNF1The performance of the electrode material in practical application is realized by using two identical FePCNF1Electrode (i.e. FePCNF)1//FePCNF1) A symmetrical supercapacitor was assembled. The electrochemical performance is shown in FIGS. 11-13. FIG. 11 is FePCNF1//FePCNF1Symmetrical capacitor at 5 mV.s-1To 100 mV. s-1Cyclic Voltammetry (CV) curves at scan rate. It can be observed that the rectangular shape is maintained without deformation at all scan rates, indicating ideal capacitive behavior. As can be seen from FIG. 12, the current density was 1 A.g-1Increased to 10A g-1The constant current charge-discharge (GCD) curve of the assembled capacitor shows good symmetry during the measurement, shows high coulombic efficiency and electrochemical reversibilityAnd (4) sex. According to
Calculating that the symmetrical super capacitor device is 1 A.g-1Has a specific capacitance of 163.1 F.g-1At 10A · g-1Can be maintained at 127F g-1. FePCNF will be at different current densities (1, 2, 3, 5, 7 and 10A g-1)1//FePCNF1The variation law of the capacitance of the capacitor device is shown in FIG. 13, and it can be seen that 1 A.g-1Change to 10A g-1The specific capacity retention rate is as high as 77.9%, which means that excellent stability is maintained throughout the charge and discharge test. By the above for FePCNF1Electrode (namely FePCNF)1//FePCNF1) The performance measurement of the assembled symmetrical super capacitor shows that the iron-based composite carbon nanofiber electrode material activated by enzyme has certain practical application value.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. Fe3O4A method for preparing porous carbon nanofibers is characterized by comprising the following steps:
s1: mixing straw liquefied carbon, polyacrylonitrile, ferric triacetylacetone and alpha-cyclodextrin to obtain a mixture, and dissolving the mixture in N, N-dimethylformamide to obtain an electrostatic spinning solution;
s2: carrying out electrostatic spinning on the electrostatic spinning solution to prepare a composite nanofiber membrane;
s3: drying the prepared composite nanofiber membrane to remove N, N-dimethylformamide, soaking in an alpha-amylase aqueous solution, sealing, heating and hydrolyzing at 70 ℃ for 90min, taking out, and washing;
s4: carrying out freeze drying and carbonization treatment on the washed composite nanofiber membrane to obtain Fe3O4Porous carbonA nanofiber material.
2. Fe of claim 13O4The preparation method of the porous carbon nanofiber is characterized in that the straw is one of hemp straw, corn straw, wheat straw, rice straw and rape straw.
3. Fe of claim 13O4The preparation method of the porous carbon nanofiber is characterized in that the mass ratio of the alpha-amylase to the alpha-cyclodextrin is 5: 1.
4. Fe of claim 13O4The preparation method of the porous carbon nanofiber is characterized in that the mass ratio of the straw liquefied carbon to the polyacrylonitrile is 1: 9.
5. Fe of claim 13O4A preparation method of porous carbon nanofiber is characterized in that the straw liquefied carbon and the polyacrylonitrile form LC-PAN.
6. Fe of claim 13O4The preparation method of the porous carbon nanofiber is characterized in that the mass ratio of the LC-PAN to the alpha-cyclodextrin is 7: 3.
7. Fe of claim 13O4The preparation method of the porous carbon nanofiber is characterized in that the mass of the ferric triacetylacetone accounts for 3% of the mass of the mixture.
8. Fe of claim 13O4The preparation method of the porous carbon nanofiber is characterized in that the carbonization treatment comprises the following steps: pre-oxidizing the freeze-dried composite nanofiber membrane in a muffle furnace at 260 ℃ for 1h at the heating rate of 1 ℃ min-1Subsequently at N2At 2 ℃ min under protection-1The rate of temperature rise of (2) is increased to 9Carbonizing at 00 deg.C for 1h, and naturally cooling.
9. Fe prepared by the method of any one of claims 1-83O4Porous carbon nanofiber materials.
10. Fe as claimed in claim 93O4Application of porous carbon nanofiber material as capacitor electrode material.
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