CN104862808A - Ferrum, nitrogen and carbon nano fiber net and production method thereof - Google Patents
Ferrum, nitrogen and carbon nano fiber net and production method thereof Download PDFInfo
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Abstract
Disclosed are a ferrum, nitrogen and carbon nano fiber net and a production method thereof. The ferrum, nitrogen and carbon nano fiber net is produced according to the following steps of, step 1, spinning solution preparation which comprises mixing ferric acetylacetonate, polyvinylpyrrolidone and ethanol and performing ultrasonic dispersion to obtain a spinning solution; step 2, electrostatic spinning; step 3, solvent atmosphere treatment which comprises placing materials obtained in the step 3 into the soluble solvent atmosphere for treatment to obtain a ferric acetylacetonate and polyvinylpyrrolidone original fiber net; step 4, pre-oxidation which comprises performing pre-oxidation in the air atmosphere; step 5, pyrolysis which comprises performing pyrolysis on a pre-oxidation fiber net and melamine to obtain a nano fiber net after carbonization; step 6, acid treatment which comprises acid treatment, washing and drying; step 7, final pyrolysis which comprises obtaining the ferrum, nitrogen and carbon nano fiber net. The production method is simple, the scale production can be achieved, the diameter distribution of the produced ferrum, nitrogen and carbon nano fiber net is uniform, the size is 200 to 500 nm, the nano fibers are connected with each other, the conductivity is good, and the application prospect is wide.
Description
Technical field
The present invention relates to a kind of fiber web and preparation method thereof, be specifically related to a kind of Fe-N-C nanometer fiber net and preparation method thereof.
Background technology
Existing low-temperature fuel cell cathode catalysis dynamics is slow, and conventional Pt/C catalyst, due to expensive and scarcity of resources, seriously restricts applying of fuel cell.And transition metal nitrogen carbon compound (M-N-C, M=Fe, Co etc.) catalytic performance is high, low price, is subject to researcher's extensive concern.Precursor pyrolysis and hot pressing has the advantages such as the Nomenclature Composition and Structure of Complexes can design and regulate and control, shaping and handling ease, is one of main method preparing ceramic composite materials at present.At present, the conventional method preparing M-N-C catalyst selects suitable carbon, nitrogen, transition metal precursor, carries out pyrolysis at a suitable temperature after mixing, and preparation technology is simple, is considered to the method for preparing catalyst of great potential.Method of electrostatic spinning is that precursor solution relies on the stretching of the high-pressure electrostatic power of several thousand to several ten thousand volts to prepare the effective ways of nanofiber; except the advantage such as possess that equipment is simple, cost is low and applicability is wide, electrospinning process is adopted to be convenient to the large-scale production realizing nanofiber.But, mutually overlap between nanofiber prepared by routine intravenous electrical spinning method, introduce contact resistance, hinder electric charge transmission between the fibers.
The people such as Yan (X. Yan, L. Gan, Y. Lin, L. Bai, T. Wang, X. Wang, J. Luo and J. Zhu, Controllable synthesis and enhanced electrocatalysis of iron-based catalysts derived from electrospun nanofibers. Small, 2014, DOI:10.1002./small.201401213.) by PAN and Fe (NO
3)
3be blended in DMF, after obtaining fibrillation felt by electrostatic spinning, direct pre-oxidation and pyrolysis, prepared Fe-N-C nanofiber overlaps mutually, contact resistance between fiber can increase electric charge transport resistance between the fibers, cause the electric conductivity of fibrofelt to decline, reduce the electro catalytic activity of fibrofelt.The people such as Jeong (B. Jeong, D. Shin, H. Jeon, J. D. Ocon, B. S. Mun, J. Baik, H. Shin and J. Lee, Excavated Fe-N-C sites for enhanced electrocatalytic acticity in the oxygen reduction reaction. ChemSusChem, 2014,7,1289-1294.) by PAN and Fe (acac)
3be blended in DMF, the nanofiber mats of preparation is after ball milling, although expose more avtive spots, fiber and the broken pore structure of fracture can hinder the transmission in the catalyst of transferring charge and electrolyte, cause the electrocatalytic oxidation reducing property of fibrofelt to reduce.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of technical process simple, be convenient to accomplish scale production, Fe-N-C nanometer fiber net that obtained nanometer fiber net is interconnected, charge transfer resistance is low and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows: a kind of Fe-N-C nanometer fiber net, makes in accordance with the following methods:
(1) spinning solution is prepared: ferric acetyl acetonade, polyvinylpyrrolidone and ethanol are added in reactor with the ratio of 0.5 ~ 6:10:100 and mix, then ultrasonic disperse, obtains spinning solution;
(2) electrostatic spinning: step (1) gained spinning solution is carried out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt;
(3) solvent atmosphere process: the suitable solvents atmosphere that step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt is placed in polyvinylpyrrolidone is processed, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net;
(4) pre-oxidation: step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net is carried out pre-oxidation in air atmosphere, obtains pre-oxidized fibers net;
(5) pyrolysis: carry out pyrolysis under step (4) gained pre-oxidized fibers net and melamine are placed in inert atmosphere protection with mass ratio 1:8 ~ 12 simultaneously, be cooled to room temperature, obtain the nanometer fiber net after carbonization;
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is carried out acid treatment, then spend deionized water to neutral, dry;
(7) final pyrolysis: the nanometer fiber net after being dried by step (6) gained carries out pyrolysis under inert atmosphere protection, is cooled to room temperature, obtains Fe-N-C nanometer fiber net.
Further, in step (3), the suitable solvents atmosphere of described polyvinylpyrrolidone refers to that the suitable solvents relative humidity of polyvinylpyrrolidone is the air atmosphere of 50 ~ 90RH%.Described relative humidity is the ratio of the saturated humidity of water or solvent at the absolute humidity of water in air or solvent and this temperature.
Further, in step (3), the temperature of described solvent atmosphere process is 15 ~ 60 DEG C (preferably 20 ~ 40 DEG C), and the time is 20 ~ 60h(preferably 22 ~ 30h).
Further, in step (3), the suitable solvents of described polyvinylpyrrolidone comprises one or more in ethanol, water or dimethyl formamide.
Through the process of step (3) suitable solvents atmosphere, the nanofiber mats of overlap joint can become interconnective nanometer fiber net under the action of the solvent mutually.
In step (1), the ratio that selected ferric acetyl acetonade, polyvinylpyrrolidone and ethanol are suitable is conducive to the fiber that electrostatic spinning obtains uniform diameter.
Further, in step (1), the K value of described polyvinylpyrrolidone is 30 ~ 90.
Further, in step (1), the frequency of described ultrasonic disperse is 15 ~ 20 kHz, and the time is 1 ~ 3h.Finely dispersed spinning solution can be obtained in this operating condition.
Further, in step (2), the technological parameter of described electrostatic spinning is as follows: adopt internal diameter to be that the metal needle of 0.5 ~ 1.5mm is as shower nozzle, spinning voltage is 12 ~ 25kV(preferably 15 ~ 20kV), needle point is 10 ~ 30cm(preferably 15 ~ 20cm to the vertical range of receiving screen), feeding rate is 5 ~ 30 μ L/min(preferably 10 ~ 20 μ L/min), spinning temperature is 10 ~ 60 DEG C (preferably 15 ~ 30 DEG C), and relative air humidity is 20 ~ 80RH%.Described receiving screen is dull and stereotyped aluminium foil.The fibre diameter obtained within the scope of above-mentioned parameter is less, and is evenly distributed.
Further, in step (4), the process of described pre-oxidation is with ramp to 240 ~ 280 DEG C of 1 ~ 5 DEG C/min, then is incubated 1 ~ 3h.It is crosslinked that pre-oxidation makes fibrillation occur, and prevent fiber from pyrolytic process, doubling phenomena occurring, suitable Pre oxidation and time can ensure that fiber is full cross-linked.
Further, in step (5), (7), the process of described pyrolysis is with ramp to 800 ~ 1000 DEG C of 1 ~ 10 DEG C/min, then is incubated 0.8 ~ 8h(preferably 1 ~ 5h).In practical operation, pre-oxidized fibers net can be covered on melamine.Described inert atmosphere is high-purity argon gas or the high pure nitrogen of purity >=99.99%.After the pyrolysis of step (5) can make pre-oxidation, fiber fully carbonizes, melamine fully decomposes distillation, nitrogen element is incorporated in fiber and forms Fe-N-C or nitrogen-doped carbon, plays electrocatalysis as avtive spot; The pyrolysis of step (7) is the small-molecule substance in order to contain in fiber after removing acidifying.
Further, in step (6), described acid treatment acid used is sulfuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1 ~ 1.0mol/L, and acid-treated temperature is 60 ~ 90 DEG C, and the time is 5 ~ 10h.Acid treatment can fiber surface contains after removing step (5) pyrolysis Fe and Fe
3o
4.
The present invention is by being dissolved in alcohol solvent by ferric acetyl acetonade and polyvinylpyrrolidone, adopt electrostatic spinning technique and polymer pyrolysis technology, through electrostatic spinning, solvent atmosphere process, pre-oxidation, pyrolysis, acid treatment and final pyrolysis, obtain porous and interconnective Fe-N-C nanometer fiber net.
Tool of the present invention has the following advantages: Fe-N-C nanofiber web preparation method is simple, is convenient to large-scale production; Fe-N-C nanometer fiber net is nonwoven fabric state, even in fiber diameter distribution, and diameter is 200 ~ 500nm; Solve for overlap joint connects between nanofiber prepared by common electrostatic spinning, cause the problem introducing contact resistance, be interconnected between Fe-N-C nanofiber network fiber of the present invention, charge transfer resistance is little; Fe-N-C in nanometer fiber net or nitrogen-doped carbon can be used as the avtive spot of electrocatalytic reaction; Fibrous inside contains abundant pore structure, and specific area is large; Prepared Fe-N-C nanometer fiber net has wide application prospects at self-supporting catalyst and fuel cell cathode catalyst field.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net;
Fig. 2 is the SEM figure of comparative example 1 gained Fe-N-C nanofiber mats;
Fig. 3 is the graph of pore diameter distribution of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net;
Fig. 4 is the full spectrogram of XPS of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net;
Fig. 5 is the electrochemical impedance spectroscopy comparison diagram of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net and comparative example 1 gained Fe-N-C nanofiber mats;
Fig. 6 is the hydrogen reduction performance comparison figure of the embodiment of the present invention 1 gained Fe-N-C nanometer fiber net and comparative example 1 gained Fe-N-C nanofiber mats.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
The embodiment of the present invention use nitrogen to be purity >=99.99% high pure nitrogen; Other chemical reagent used, if no special instructions, is all obtained by routine business approach.
embodiment 1
(1) spinning solution is prepared: by ferric acetyl acetonade, polyvinylpyrrolidone (K value is 90) and ethanol with the mixing of the ratio of mass ratio 2:10:100, then under 20 kHz supersonic frequencies, carry out ultrasonic disperse 2h, obtain spinning solution;
(2) electrostatic spinning: adopt internal diameter to be that the metal needle of 0.8mm is as shower nozzle, spinning voltage is 15kV, needle point is 15cm to the vertical range of receiving screen, feeding rate is 15 μ L/min, spinning temperature is 20 DEG C, relative air humidity is 40RH%, silk received by dull and stereotyped aluminium foil, and step (1) gained spinning solution is carried out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt;
(3) solvent atmosphere process: step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt is placed in malaria atmosphere, the relative humidity of steam is 70RH%, the temperature of process is 25 DEG C, and the time is 24h, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net;
(4) pre-oxidation: step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net is placed in pre-oxidation furnace, in air atmosphere, with the ramp to 260 DEG C of 3 DEG C/min, then is incubated 2h and carries out pre-oxidation treatment, obtain pre-oxidized fibers net;
(5) pyrolysis: step (4) gained pre-oxidized fibers net and melamine are placed in pyrolysis oven with mass ratio 1:10 simultaneously, under nitrogen protection, with the ramp to 900 DEG C of 5 DEG C/min, then be incubated 2h and carry out pyrolysis, be cooled to room temperature, obtain the nanometer fiber net after carbonization;
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is placed in the H that concentration is 0.5mol/L
2sO
4in solution, at 80 DEG C, carry out acid treatment 8h, then spend deionized water to neutral, dry;
(7) final pyrolysis: the nanometer fiber net after being dried by step (6) gained is placed in pyrolysis oven, under nitrogen protection, with the ramp to 900 DEG C of 5 DEG C/min, then is incubated 1h and carries out pyrolysis, be cooled to room temperature, obtain Fe-N-C nanometer fiber net.
As shown in Figure 1, be interconnected between the nanofiber of the Fe-N-C nanometer fiber net obtained by the embodiment of the present invention, namely part melting under solvent action of fiber overlap joint is integrated, for transferring charge provides continuous passage, fibre diameter size is 250 ~ 300 nm, after testing, its surface is in loose structure, and pore structure is mainly mesoporous (as shown in Figure 3), is conducive to electrolyte and transmits at fibrous inside, improve electrocatalysis characteristic; As shown in Figure 4, Fe-N-C nanometer fiber net is primarily of C, Fe, O and N element composition, Fe-N-C and N-C key wherein can, as the avtive spot of electrocatalytic reaction, contribute to improving electrocatalytic oxidation reducing property.
embodiment 2
(1) spinning solution is prepared: by ferric acetyl acetonade, polyvinylpyrrolidone (K value is 30) and ethanol with the mixing of the ratio of mass ratio 5:10:100, then under 15 kHz supersonic frequencies, carry out ultrasonic disperse 3h, obtain spinning solution;
(2) electrostatic spinning: adopt internal diameter to be that the metal needle of 0.8mm is as shower nozzle, spinning voltage is 20kV, needle point is 20cm to the vertical range of receiving screen, feeding rate is 10 μ L/min, spinning temperature is 20 DEG C, relative air humidity is 20RH%, silk received by dull and stereotyped aluminium foil, and step (1) gained spinning solution is carried out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt;
(3) solvent atmosphere process: step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt is placed in the dry air atmosphere containing ethanol, the relative humidity of alcohol vapor is 50RH%, the temperature of process is 25 DEG C, time is 24h, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net;
(4) pre-oxidation: step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net is placed in pre-oxidation furnace, in air atmosphere, with the ramp to 280 DEG C of 1 DEG C/min, then is incubated 1h and carries out pre-oxidation treatment, obtain pre-oxidized fibers net;
(5) pyrolysis: step (4) gained pre-oxidized fibers net and melamine are placed in pyrolysis oven with mass ratio 1:10 simultaneously, under nitrogen protection, with the ramp to 800 DEG C of 10 DEG C/min, then be incubated 2h and carry out pyrolysis, be cooled to room temperature, obtain the nanometer fiber net after carbonization;
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is placed in the HCl solution that concentration is 1.0 mol/L, at 60 DEG C, carries out acid treatment 10h, then spend deionized water to neutral, dry;
(7) final pyrolysis: the nanometer fiber net after being dried by step (6) gained is placed in pyrolysis oven, under nitrogen protection, with the ramp to 800 DEG C of 10 DEG C/min, then is incubated 1h and carries out pyrolysis, be cooled to room temperature, obtain Fe-N-C nanometer fiber net.
Be interconnected between the nanofiber of the Fe-N-C nanometer fiber net obtained by the embodiment of the present invention, namely part melting under solvent action of fiber overlap joint is integrated, and for transferring charge provides continuous passage, fibre diameter size is 220 ~ 260 nm; After testing, its surface is in loose structure, and pore structure is mainly mesoporous, is conducive to electrolyte and transmits at fibrous inside, improves electrocatalysis characteristic; Fe-N-C nanometer fiber net prepared by this example is primarily of C, Fe, O and N element composition, Fe-N-C and N-C key wherein can play electrocatalysis as the avtive spot of electrocatalytic reaction.The peak current density J of Fe-N-C nanometer fiber net
p=1.10mAcm
-2, illustrate the electron transport ability of interconnective Fe-N-C nanoweb structures and electro catalytic activity high.
comparative example 1
This comparative example preparation technology is with embodiment 1, and its difference is only: do not carry out step (3) solvent atmosphere process, and final products therefrom is Fe-N-C nanofiber mats.
As shown in Figure 1, be interconnected between the nanofiber of the Fe-N-C nanometer fiber net obtained by the embodiment of the present invention 1, namely part melting under solvent action of fiber overlap joint is integrated, as shown in Figure 2, be nonwoven fabric distributions without fiber in the Fe-N-C nanofiber mats of comparative example 1 gained of solvent atmosphere process, diameter is evenly distributed, and mutually overlaps between nanofiber; The electrochemical impedance spectroscopy comparative analysis of the Fe-N-C nanometer fiber net obtained by embodiment in Fig. 51 and the Fe-N-C nanofiber mats obtained by comparative example 1, the transferring charge resistance of Fe-N-C nanometer fiber net is 4.3 Ω, the transferring charge resistance of Fe-N-C nanofiber mats is 7.0 Ω, illustrates that interconnective nanoweb structures effectively can reduce electric charge transport resistance in the fibre; As shown in Figure 6, through the test of electrocatalytic oxidation reduction reaction, the peak current density J of the Fe-N-C nanometer fiber net obtained by embodiment 1
p=1.02mAcm
-2, higher than the J of the Fe-N-C nanofiber mats obtained by comparative example 1
p=0.76mAcm
-2, the electron transport ability of the Fe-N-C nanometer fiber net being interconnected structure and the electro catalytic activity nanofiber mats higher than bridging arrangement can be described equally.
Claims (10)
1. a Fe-N-C nanometer fiber net, is characterized in that, makes in accordance with the following methods:
(1) spinning solution is prepared: ferric acetyl acetonade, polyvinylpyrrolidone and ethanol are added in reactor with the ratio of 0.5 ~ 6:10:100 and mix, then ultrasonic disperse, obtains spinning solution;
(2) electrostatic spinning: step (1) gained spinning solution is carried out electrostatic spinning, collects ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt;
(3) solvent atmosphere process: the suitable solvents atmosphere that step (2) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation felt is placed in polyvinylpyrrolidone is processed, obtains ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net;
(4) pre-oxidation: step (3) gained ferric acetyl acetonade/polyvinylpyrrolidone fibrillation net is carried out pre-oxidation in air atmosphere, obtains pre-oxidized fibers net;
(5) pyrolysis: carry out pyrolysis under step (4) gained pre-oxidized fibers net and melamine are placed in inert atmosphere protection with mass ratio 1:8 ~ 12 simultaneously, be cooled to room temperature, obtain the nanometer fiber net after carbonization;
(6) acid treatment: the nanometer fiber net after step (5) gained carbonization is carried out acid treatment, then spend deionized water to neutral, dry;
(7) final pyrolysis: the nanometer fiber net after being dried by step (6) gained carries out pyrolysis under inert atmosphere protection, is cooled to room temperature, obtains Fe-N-C nanometer fiber net.
2. Fe-N-C nanometer fiber net according to claim 1, it is characterized in that: in step (3), the suitable solvents atmosphere of described polyvinylpyrrolidone refers to that the suitable solvents relative humidity of polyvinylpyrrolidone is the air atmosphere of 50 ~ 90RH%.
3. Fe-N-C nanometer fiber net according to claim 1 or 2, is characterized in that: in step (3), and the temperature of described solvent atmosphere process is 15 ~ 60 DEG C, and the time is 20 ~ 60h.
4. according to the described Fe-N-C nanometer fiber net of one of claims 1 to 3, it is characterized in that: in step (3), the suitable solvents of described polyvinylpyrrolidone comprises one or more in ethanol, water or dimethyl formamide.
5. according to the described Fe-N-C nanometer fiber net of one of Claims 1 to 4, it is characterized in that: in step (1), the K value of described polyvinylpyrrolidone is 30 ~ 90.
6. according to the described Fe-N-C nanometer fiber net of one of Claims 1 to 5, it is characterized in that: in step (1), the frequency of described ultrasonic disperse is 15 ~ 20 kHz, and the time is 1 ~ 3h.
7. according to the described Fe-N-C nanometer fiber net of one of claim 1 ~ 6, it is characterized in that: in step (2), the technological parameter of described electrostatic spinning is as follows: adopt internal diameter to be that the metal needle of 0.5 ~ 1.5mm is as shower nozzle, spinning voltage is 12 ~ 25kV, needle point is 10 ~ 30cm to the vertical range of receiving screen, feeding rate is 5 ~ 30 μ L/min, and spinning temperature is 10 ~ 60 DEG C, and relative air humidity is 20 ~ 80RH%.
8. according to the described Fe-N-C nanometer fiber net of one of claim 1 ~ 7, it is characterized in that: in step (4), the process of described pre-oxidation is with ramp to 240 ~ 280 DEG C of 1 ~ 5 DEG C/min, then is incubated 1 ~ 3h.
9. according to the described Fe-N-C nanometer fiber net of one of claim 1 ~ 8, it is characterized in that: in step (5), (7), the process of described pyrolysis is with ramp to 800 ~ 1000 DEG C of 1 ~ 10 DEG C/min, then is incubated 0.8 ~ 8h.
10. according to the described Fe-N-C nanometer fiber net of one of claim 1 ~ 9, it is characterized in that: in step (6), described acid treatment acid used is sulfuric acid, nitric acid or hydrochloric acid, and the concentration of acid is 0.1 ~ 1.0mol/L, acid-treated temperature is 60 ~ 90 DEG C, and the time is 5 ~ 10h.
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Cited By (3)
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CN106784890A (en) * | 2016-12-07 | 2017-05-31 | 深圳大学 | A kind of fuel cell non-precious metal catalyst and preparation method thereof and fuel cell |
CN107974734A (en) * | 2017-11-24 | 2018-05-01 | 合肥工业大学 | A kind of preparation method of the porous carbon fiber of Fe/N doping |
CN108914153A (en) * | 2018-06-08 | 2018-11-30 | 深圳大学 | A kind of nitrogen-doped carbon nano-fiber elctro-catalyst and the preparation method and application thereof |
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NICHOLAS LAROUCHE ET AL.: "《Activity and stability in proton exchange membrane fuel cells of iron-based cathode catalysts synthesized with addition of carbon fibers》", 《ELECTROCHIMICA ACTA》 * |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106784890A (en) * | 2016-12-07 | 2017-05-31 | 深圳大学 | A kind of fuel cell non-precious metal catalyst and preparation method thereof and fuel cell |
CN107974734A (en) * | 2017-11-24 | 2018-05-01 | 合肥工业大学 | A kind of preparation method of the porous carbon fiber of Fe/N doping |
CN107974734B (en) * | 2017-11-24 | 2020-10-02 | 合肥工业大学 | Preparation method of Fe/N-doped porous carbon fiber |
CN108914153A (en) * | 2018-06-08 | 2018-11-30 | 深圳大学 | A kind of nitrogen-doped carbon nano-fiber elctro-catalyst and the preparation method and application thereof |
CN108914153B (en) * | 2018-06-08 | 2020-07-17 | 深圳大学 | Nitrogen-doped carbon nanofiber electrocatalyst and preparation method and application thereof |
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