CN110164703A - Porous Fe3O4/ C faceted material and its preparation method and application - Google Patents
Porous Fe3O4/ C faceted material and its preparation method and application Download PDFInfo
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- CN110164703A CN110164703A CN201910546562.9A CN201910546562A CN110164703A CN 110164703 A CN110164703 A CN 110164703A CN 201910546562 A CN201910546562 A CN 201910546562A CN 110164703 A CN110164703 A CN 110164703A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007772 electrode material Substances 0.000 claims abstract description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003990 capacitor Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 1
- UQPKFUZWTGSHJD-UHFFFAOYSA-N CO.O.O.O.O.O.O.[N+](=O)(O)[O-] Chemical compound CO.O.O.O.O.O.O.[N+](=O)(O)[O-] UQPKFUZWTGSHJD-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
- H01G11/46—Metal oxides
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of porous Fes3O4/ C faceted material and its preparation method and application.The present invention uses ZIF-67 for hard template, obtains carbon polyhedron by carbonization and pickling.Using carbon polyhedron as secondary template, with Fe (CH3COO)2, thiocarbamide is oxidant, and water is that solvent carries out isothermal reaction.Product is centrifuged and obtains a kind of ferroferric oxide/carbon micro-nano material with polyhedral structure after being calcined under air.This micro-nano material has high specific surface area, and particle is uniformly dispersed, is conducive to the quick transmission of ion, increases surface-active site.After tested, in 2 A g‑1Current density under recycle its specific capacity after 3000 times and still can reach 571.7 F g‑1And higher energy density can still be maintained under high power density.Therefore, the porous ferroferric oxide/carbon polyhedron can carry out practical application as the electrode material of supercapacitor.
Description
Technical field
The invention belongs to supercapacitor technologies fields, and in particular to porous Fe3O4/ C faceted material and preparation method thereof
And application.
Background technique
The energy storage mechnism of supercapacitor can be divided into electric double layer capacitance and Faraday pseudo-capacitance.Using Faraday pseudo-capacitance as machine
The supercapacitor of reason is due to occurring redox reaction at the phase interface of electrode material and electrolyte, specific capacity is better than double electricity
The supercapacitor of layer capacitance energy storage.Therefore, more paid close attention to by people with the electrode material of Faraday pseudo-capacitance energy storage and
Research.
Currently, the electrode material of the supercapacitor based on Faraday pseudo-capacitance is mostly with metal oxide and its combination electrode
Based on material.
Although the oxide of metal oxide, especially iron has higher specific capacity, but its poor electric conductivity limits
Its development.Metal oxide, which can occur to reunite, during fast charging and discharging hinders the charge of electrolyte and electrode surface to pass
It is defeated.Therefore, metal oxide has lower power density and high rate performance as the electrode material of supercapacitor, is difficult to answer
In actual production practice.Therefore metal oxide often with carbon material it is compound with improve electrode material entirety electric conductivity and
Stability.At this stage the study found that this kind of composite material can be realized the synergistic effect between the two performance, obtain composite material
Higher electrochemical capacitor, excellent high rate performance and preferable cyclical stability.
Influence electrochemical capacitor performance is not only the microstructure of the composition also electrode material of electrode material.Although
Electrode material can increase specific surface area after by nanosizing to a certain extent, provide more surface capacitance storage
Active site.But it will lead to nanoparticle agglomerates by prolonged charge and discharge cycles, so as to cause active site reduction, electrode
Charge mass transfer between surface and electrolyte is suppressed.
Summary of the invention
Goal of the invention: technical problem to be solved by the invention is to provide Fe3O4/ C faceted material.
Also there is provided Fe for technical problems to be solved by the present invention3O4The preparation method of/C faceted material, the present invention use
Template obtains a kind of ferroferric oxide/carbon polyhedron micro-nano multilevel structure with high-specific surface area, and the composite material is aobvious
The specific capacitance for improving iron oxide based super capacitor and cycle life are write (in 2Ag-1Current density under recycle 3000 times after,
Specific capacitance stills remain in 571.7F g-1And specific capacitance conservation rate is 88.8% or more), it yet there are no relevant report.
Also there is provided Fe for technical problems to be solved by the present invention3O4The application of/C faceted material.The material is for super
The electrode material of capacitor has biggish specific surface area, good high rate performance and stability, high-power charge and discharge is suitble to make
With.
There is provided a kind of supercapacitors using above-mentioned composite material for the last technical problems to be solved of the present invention.
Technical solution: in order to solve the above-mentioned technical problem, this invention takes the following technical solutions: a kind of porous
Fe3O4/ C faceted material, which is characterized in that institute's porous Fe3O4The X-ray diffraction key data of/C faceted material: 18.99
± 0.5 ° of .31.2 ± 0.5 °, 36.8 ± 0.5 °, 38.5 ± 0.5 °, 44.8 ± 0.5 °, 55.6 ± 0.5 °, 59.3 ± 0.5 °, 65.2
There is Fe at ± 0.5 °3O4Characteristic peak, corresponding d spacing is4.67 ± 0.1,2.86 ± 0.1,2.44 ± 0.1,
2.34 ± 0.1,2.02 ± 0.1,1.65 ± 0.1,1.58 ± 0.1,1.43 ± 0.1, the peak position of above-mentioned appearance is corresponding opposite
Intensity % is 12.9 ± 0.5,31.9 ± 0.5,100.0,9.3 ± 0.5,23.8 ± 0.5,10.7 ± 0.5,31.6 ± 0.5,34.9
±0.5.It is worth noting that, occurring the characteristic peak that fluctuation is agraphitic carbon at 23.5 ± 0.5 °.
Wherein, the porous Fe3O4/ C faceted material is micron-nanometer multi structure.
Wherein, the porous Fe3O4/ C faceted material is porous Fe3O4The specific surface area of/C faceted material
123.32m2g-1~547.51m2g-1。
Wherein, the porous Fe3O4Element ratio=1~1.5 that/C faceted material is Fe: O: C: 2: 1.
The content of present invention further includes the porous Fe3O4The preparation method of/C faceted material, comprising the following steps:
1) polyhedron carbon is added to containing Fe (CH3COO)2And in the aqueous solution of thiocarbamide, by gained mixture at 80~90 DEG C
9~12h of hydro-thermal reaction is carried out, Fe is obtained2O3/ C composite drying for standby；
2) by Fe obtained by step 1)2O3/ C composite 400~500 DEG C of heat preservation 2-4h in air, it is cooling to obtain the final product.
Wherein, the polyhedron carbon is prepared by following methods: by 700~800 DEG C under a nitrogen of ZIF-67 polyhedron
3~4h of calcining obtains Co/C polyhedron, is washed till Co ion with the hydrochloric acid of 4-12M later and completely removes to obtain the final product.
Wherein, salt pickling actual conditions are as follows: stir 2h under the conditions of 25~30 DEG C, 5~8 times repeatedly, after be washed to neutrality,
It is drying to obtain.
Wherein, the mass ratio of Co/C polyhedron and hydrochloric acid is 1: 1000, and dry temperature is 80 DEG C.
Wherein, the Fe (CH in the step 1)3COO)2: thiocarbamide: the mass ratio of water is 1-2: 2~4: 100.
The content of present invention further includes the porous Fe3O4/ C faceted material is in preparing electrode material for super capacitor
Using.
The content of present invention further includes a kind of super capacitance electrode material, and the super capacitance electrode material includes described more
Hole Fe3O4/ C faceted material.
Wherein, the super capacitance electrode material 2Ag-1Current density under recycle 3000 its specific capacities 307.3~
571.7Fg-1。
The utility model has the advantages that compared with the existing technology, the invention has the following advantages that porous ferroferric oxide/carbon of the invention
Polyhedral electrode material for super capacitor is micron-nanometer multi structure, has biggish specific surface area (547.51m2g-1)
It is capable of providing more surface-active site.Ferroso-ferric oxide and carbon material it is compound can play between the two cooperate with effect
It answers, i.e., is the counterfeit electricity of redox of ferroso-ferric oxide using the preferable electric conductivity of carbon material and the electric double layer effect of storeroom
Appearance behavior provides stable electron channel, and ferroso-ferric oxide is enable to realize height ratio capacity to greatest extent under high current density.
Combination electrode is set to obtain higher discharge voltage, the whole energy density and power density for improving electrode material.
Detailed description of the invention
Carbon polyhedron and porous Fe made from Fig. 1 embodiment 13O4The polyhedral scanning electron microscope diagram of/C (SEM)；
Carbon polyhedron and porous Fe made from Fig. 2 embodiment 13O4The polyhedral transmission electron microscope figure of/C (TEM)；
Carbon polyhedron and porous Fe made from Fig. 3 embodiment 13O4The polyhedral X ray diffracting spectrum of/C (XRD), wherein a
For carbon polyhedron, b is porous Fe3O4/ C faceted material；
Fig. 4 is in current density 2Ag-1When porous Fe3O4The charge and discharge cycles figure of/C faceted material.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described, so that professional technician more fully understands this
Invention, but it is not limited to following embodiment.
The polyhedral synthesis step of ZIF-67 in the embodiment of the present invention includes: to weigh 249.0mg Co (NO3)2·6H2O
It is dissolved in 25.0mL methanol respectively with 328.0mg 2-methylimidazole.Next, latter 2-methylimidazole methanol solution is delayed
Slow be added in former pink cabaltous nitrate hexahydrate methanol solution obtains mixture, and mixture is ultrasonically treated at room temperature
Obtain solution within 10 minutes.Then solution is mixed and stands 24 hours and by the way that sediment is collected by centrifugation, with methanol wash for several times,
It is dried in vacuo 24 hours at 80 DEG C, obtains ZIF-67 polyhedron.
1 porous Fe of embodiment3O4The polyhedral preparation of/C
400mg ZIF-67 polyhedron is put into quartz boat, is placed into tube furnace.By tube furnace with 3 DEG C of min-1Heating
It makes annealing treatment 4 hours to 700 DEG C and in a nitrogen atmosphere, and cooled to room temperature obtains Co/C.Obtained Co/C is placed in
4mol L-112 hours to wash away metallic cobalt, finally obtain polyhedron carbon in HCl.
Configure 30mL50mmol.L-1Fe(CH3COO)2Aqueous solution, then thereto be added 60mg polyhedron carbon, first surpass
Sound 0.5h, then magnetic agitation 0.5h obtains dispersion liquid.The thiocarbamide of 0.5g is added into above-mentioned dispersion liquid, continues to stir 0.5h,
12h is heated in 90 DEG C of water-bath, is then centrifuged for obtaining Fe2O3/ C presoma, dries 10h at 80 DEG C.After drying
Fe2O3/ C presoma is put into quartz boat, is placed in tube furnace.Diamond heating is kept to 500 DEG C and in air atmosphere
(heating rate is 1 DEG C of min to 4h-1), remove Fe2O3Carbon and cooled to room temperature in/C obtain porous Fe3O4/ C polyhedron,
Its specific surface area is 547.51m2g-1。
2 porous Fe of embodiment3O4The polyhedral preparation of/C
400mg ZIF-67 polyhedron is put into quartz boat, is placed into tube furnace.By tube furnace with 3 DEG C of min-1Heating
It makes annealing treatment 4 hours to 700 DEG C and in a nitrogen atmosphere, and cooled to room temperature obtains Co/C.Co/C will be obtained to be placed in
4mol L-112 hours to wash away metallic cobalt, finally obtain polyhedron carbon in HCl.
Configure 30mL 25mmolL-1Fe(CH3COO)2Aqueous solution, then thereto be added 30mg polyhedron carbon, first
Ultrasonic 0.5h, then magnetic agitation 0.5h obtains dispersion liquid.The thiocarbamide of 0.25g is added into dispersion liquid, continues to stir 0.5h,
12h is heated in 90 DEG C of water-bath, is then centrifuged for obtaining Fe2O3/ C presoma, dries 10h at 80 DEG C.By the Fe of drying2O3/
C presoma is put into quartz boat, is placed in tube furnace.4h is kept (to rise to 500 DEG C and in air atmosphere diamond heating
Warm rate is 1 DEG C of min-1), remove Fe2O3Carbon and cooled to room temperature in/C obtain porous Fe3O4/ C polyhedron.
3 porous Fe of embodiment3O4The polyhedral preparation of/C
400mg ZIF-67 polyhedron is put into quartz boat, is placed into tube furnace.By tube furnace with 3 DEG C of min-1Heating
It makes annealing treatment 4 hours to 700 DEG C and in a nitrogen atmosphere, and cooled to room temperature obtains Co/C.Co/C will be obtained to be placed in
4mol L-112 hours to wash away metallic cobalt, finally obtain polyhedron carbon in HCl.
Configure 50mL 100mmolL-1Fe(CH3COO)2Aqueous solution, then thereto be added 120mg polyhedron carbon,
First ultrasound 0.5h, then magnetic agitation 0.5h obtains dispersion liquid.The thiocarbamide of 1.0g is added into above-mentioned dispersion liquid, continues to stir
0.5h heats 12h in 90 DEG C of water-bath, is then centrifuged for obtaining Fe2O3/ C presoma, dries 10h at 80 DEG C.It will obtain
Fe2O3/ C presoma is put into quartz boat, is placed in tube furnace.Diamond heating is protected to 500 DEG C and in air atmosphere
Holding 4h, (heating rate is 1 DEG C of min-1), remove Fe2O3Carbon and cooled to room temperature in/C obtain porous Fe3O4/ C multi-panel
Body.
4 porous Fe of embodiment3O4The polyhedral preparation of/C
400mg ZIF-67 polyhedron is put into quartz boat, is placed into tube furnace.By tube furnace with 1 DEG C of min-1Heating
It makes annealing treatment 4 hours to 700 DEG C and in a nitrogen atmosphere, and cooled to room temperature obtains Co/C.Co/C will be obtained to be placed in
4mol L-112 hours to wash away metallic cobalt, finally obtain polyhedron carbon in HCl.
Configure 30mL 50mmolL-1Fe(CH3COO)2Aqueous solution, then thereto be added 60mg polyhedron carbon, first
Ultrasonic 0.5h, then magnetic agitation 0.5h obtains dispersion liquid.The thiocarbamide of 0.5g is added into above-mentioned dispersion liquid, continues to stir
0.5h heats 12h in 90 DEG C of water-bath, is then centrifuged for obtaining Fe2O3/ C presoma, dries 10h at 80 DEG C.It will obtain
Fe2O3/ C presoma is put into quartz boat, is placed in tube furnace.Diamond heating is protected to 400 DEG C and in air atmosphere
Holding 4h, (heating rate is 1 DEG C of min-1), remove Fe2O3Carbon and cooled to room temperature in/C obtain porous Fe3O4/ C multi-panel
Body.
5 porous Fe of embodiment3O4The polyhedral preparation of/C
400mg ZIF-67 polyhedron is put into quartz boat, is placed into tube furnace.By tube furnace with 3 DEG C of min-1Heating
It makes annealing treatment 4 hours to 700 DEG C and in a nitrogen atmosphere, and cooled to room temperature obtains Co/C.Co/C will be obtained to be placed in
4mol L-112 hours to wash away metallic cobalt, finally obtain polyhedron carbon in HCl.
Configure 50mL 50mmolL-1Fe(CH3COO)2Aqueous solution, then thereto be added 60mg polyhedron carbon, first
Ultrasonic 0.5h, then magnetic agitation 0.5h obtains dispersion liquid.The thiocarbamide of 0.5g is added into above-mentioned dispersion liquid, continues to stir
0.5h heats 12h in 90 DEG C of water-bath, is then centrifuged for obtaining Fe2O3/ C presoma, dries 10h at 60 DEG C.It will obtain
Fe2O3/ C presoma is put into quartz boat, is placed in tube furnace.Diamond heating is protected to 500 DEG C and in air atmosphere
Holding 4h, (heating rate is 1 DEG C of min-1), remove Fe2O3Carbon and cooled to room temperature in/C obtain porous Fe3O4/ C multi-panel
Body.
6 porous Fe of embodiment3O4The polyhedral preparation of/C
400mg ZIF-67 polyhedron is put into quartz boat, is placed into tube furnace.By tube furnace with 3 DEG C of min-1Heating
It makes annealing treatment 4 hours to 700 DEG C and in a nitrogen atmosphere, and cooled to room temperature obtains Co/C.Co/C will be obtained to be placed in
4mol L-112 hours to wash away metallic cobalt, finally obtain polyhedron carbon in HCl.
Configure 50mmolL-1Fe(CH3COO)2Aqueous solution, then thereto be added 60mg polyhedron carbon, first ultrasound
0.5h, then magnetic agitation 0.5h obtains dispersion liquid.The thiocarbamide of 0.5g is added into above-mentioned dispersion liquid, continues to stir 0.5h,
10h is heated in 90 DEG C of water-bath, is then centrifuged for obtaining Fe2O3/ C presoma, dries 10h at 80 DEG C.The Fe that will be obtained2O3/
C presoma is put into quartz boat, is placed in tube furnace.4h is kept (to rise to 500 DEG C and in air atmosphere diamond heating
Warm rate is 1 DEG C of min-1), remove Fe2O3Carbon and cooled to room temperature in/C obtain porous Fe3O4/ C polyhedron, compares table
Area is 123.32m2g-1。
The preparation of 7 electrode material for super capacitor of embodiment
Acetylene black is used to make conductive agent, polyvinylidene fluoride (PVDF) as binder, it respectively will be more in Examples 1 to 6
Hole Fe3O4/ C polyhedron active material, acetylene black conductor and Kynoar (PVDF) binder are with 8: 1: 1 mass ratio
It is uniformly mixed, 200 μ L N-Methyl pyrrolidones is added and make solvent, the ultrasound 6-8h in ultrasonic machine, the nickel foam that is coated in that treated
(1×1cm2) surface, the nickel foam for loading active substance is then placed in 120 DEG C of vacuum ovens dry removal solvent,
Finally in 10MPa pressure lower sheeting, working electrode can be obtained.
The performance test of experimental example electrode material for super capacitor
By embodiment 7 prepare with porous Fe in load embodiment 1-63O4The polyhedral nickel foam of/C is working electrode, platinum
Piece is to electrode, and Hg/HgO is reference electrode, and the test of supercapacitor correlated performance is carried out in the KOH solution of 3.0M.
Examples 1 to 6 porous Fe as can be seen from Figure 13O4/ C polyhedron maintains the pattern of carbon polyhedron template, institute substantially
Composite material surface obtained is coarse, and coarse surface can increase surface area, provides more for electrochemical redox reaction
Active site.
Examples 1 to 6 porous Fe as can be seen from Figure 23O4/ C polyhedron is made of the little particle of 20nm, is had microcosmic porous
Structure.Porous structure is conducive to the infiltration of electrolyte and the transmission of ion, further promotes electrochemical reaction dynamics.
Examples 1 to 6 porous Fe as can be seen from Figure 33O4The polyhedral XRD diffraction maximum of/C and Fe3O4Standard card PDF
(#26-1136) diffraction maximum position consistency, in the characteristic peak that 25 ° or so of fluctuations are agraphitic carbon.
1 porous Fe of embodiment as can be seen from Figure 43O4/ C polyhedron is as electrode material for super capacitor in 2Ag-1Electric current
Charge and discharge cycles 3000 times under density, specific capacity can still be maintained in 571.7F g-1Show electrode energy with higher
Metric density and preferable cycle performance；And the porous Fe that embodiment 2~6 synthesizes3O4/ C polyhedron is the material of supercapacitor
Its specific capacitance is respectively 319.6F g after charge and discharge cycles 3000 times-1, 403.1F g-1, 418.8F g-1, 428.9F g-1,
307.3F g-1, compared with Example 1, specific capacitance is relatively low.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of porous Fe3O4/ C faceted material, which is characterized in that the porous Fe3O4The X-ray of/C faceted material is spread out
Penetrate key data: 18.99 ± 0.5 °, 31.2 ± 0.5 °, 36.8 ± 0.5 °, 38.5 ± 0.5 °, 44.8 ± 0.5 °, 55.6 ±
There is Fe at 0.5 °, 59.3 ± 0.5 °, 65.2 ± 0.5 °3O4Characteristic peak, corresponding d spacing are as follows: 4.67 ± 0.1,
2.86 ± 0.1,2.44 ± 0.1,2.34 ± 0.1,2.02 ± 0.1,1.65 ± 0.1,1.58 ± 0.1,1.43 ± 0.1, it is above-mentioned go out
The corresponding relative intensity % in existing peak position is 12.9 ± 0.5,31.9 ± 0.5,100.0,9.3 ± 0.5,23.8 ± 0.5,10.7
± 0.5,31.6 ± 0.5,34.9 ± 0.5.
2. porous Fe according to claim 13O4/ C faceted material, which is characterized in that the porous Fe3O4/ C polyhedron
Material is micron-nanometer multi structure.
3. porous Fe according to claim 13O4/ C faceted material, which is characterized in that the porous Fe3O4/ C polyhedron
Material is porous Fe3O4123.32 m of specific surface area of/C faceted material2 g-1~ 547.51 m2 g-1。
4. porous Fe according to claim 13O4/ C faceted material, which is characterized in that the porous Fe3O4/ C polyhedron
Material is element ratio=1 ~ 1.5:2:1 of Fe:O:C.
5. the described in any item porous Fes of claim 1 ~ 43O4The preparation method of/C faceted material, which is characterized in that including with
Lower step:
1) polyhedron carbon is added to containing Fe (CH3COO)2And in the aqueous solution of thiocarbamide, gained mixture is carried out at 80 ~ 90 DEG C
9 ~ 12 h of hydro-thermal reaction, obtains Fe2O3/ C composite drying for standby；
2) by Fe obtained by step 1)2O3/ C composite 400 ~ 500 DEG C of 2 ~ 4 h of heat preservation in air, it is cooling to obtain the final product.
6. porous Fe according to claim 53O4The preparation method of/C faceted material, which is characterized in that the polyhedron
Carbon is prepared by following methods: by ZIF-67 polyhedron 700 ~ 800 DEG C of 3 ~ 4 h of calcining under a nitrogen, later with 4 ~ 12 M's
Hydrochloric acid is washed till Co ion and completely removes to obtain the final product.
7. porous Fe according to claim 53O4The preparation method of/C faceted material, which is characterized in that the step
1) Fe (CH in3COO)2: thiocarbamide: the mass ratio of water is 1 ~ 2:2 ~ 4:100.
8. any one of claim 1 ~ 4 porous Fe3O4/ C faceted material is preparing answering in electrode material for super capacitor
With.
9. a kind of super capacitance electrode material, which is characterized in that the super capacitance electrode material includes that claim 1 ~ 4 is any
Porous Fe described in3O4/ C faceted material.
10. super capacitance electrode material according to claim 9, which is characterized in that 2 A of super capacitance electrode material
g-1Current density under recycle 3000 its specific capacities be 307.3 ~ 571.7 F g-1。
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