CN110164703B - Porous Fe3O4/C polyhedral material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses porous Fe3O4a/C polyhedral material and a preparation method and application thereof. According to the invention, ZIF-67 is used as a hard template, and the carbon polyhedron is obtained through carbonization and acid washing. Using carbon polyhedron as secondary template and Fe (CH)3COO)2Thiourea is used as an oxidant, and water is used as a solvent to carry out constant temperature reaction. Centrifuging the product and calcining the product in the air to obtain the ferroferric oxide/carbon micro-nano material with a polyhedral structure. The micro-nano material has high specific surface area and uniformly dispersed particles, is favorable for the rapid transmission of ions, and increases surface active sites. Tested at 2A g‑1The specific capacity of the alloy can still reach 571.7F g after the alloy is cycled for 3000 times under the current density‑1And still be able to maintain a higher energy density at high power densities. Therefore, the porous ferroferric oxide/carbon polyhedron can be practically applied as an electrode material of a supercapacitor.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to porous Fe3O4a/C polyhedral material and a preparation method and application thereof.
Background
The energy storage mechanism of the super capacitor can be divided into electric double layer capacitance and Faraday pseudo capacitance. The super capacitor with the Faraday pseudocapacitance as the mechanism has specific capacity superior to that of super capacitor with double electric layer capacitance energy storage because of the oxidation-reduction reaction of the electrode material and the electrolyte at the phase interface. Therefore, electrode materials for storing energy by faraday pseudocapacitance are receiving more attention and research.
At present, the electrode material of the super capacitor based on the Faraday pseudocapacitance is mainly metal oxide and the composite electrode material thereof.
Metal oxides, particularly iron oxides, while having a high specific capacity, their poor conductivity limits their development. During the rapid charge and discharge process, the metal oxide can agglomerate to block the charge transmission between the electrolyte and the electrode surface. Therefore, the metal oxide has lower power density and rate capability as the electrode material of the super capacitor, and is difficult to be applied to practical production practice. Therefore, the metal oxide is often combined with a carbon material to improve the conductivity and stability of the electrode material as a whole. The research in the present stage finds that the composite material can realize the synergistic effect between the performances of the two materials, so that the composite material can obtain higher electrochemical capacitance, excellent rate performance and better cycle stability.
It is not only the composition of the electrode material but also the microstructure of the electrode material that influences the electrochemical capacitance behavior. Although the electrode material can increase the specific surface area to a certain extent after being subjected to nanocrystallization, more active sites for surface capacitance storage are provided. However, after long-time charge-discharge circulation, the nano particles are agglomerated, so that the active sites are reduced, and the charge transfer between the electrode surface and the electrolyte is inhibited.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide Fe3O4a/C polyhedral material.
The technical problem to be solved by the invention is to provide Fe3O4The invention relates to a preparation method of a/C polyhedral material, which adopts a template method to obtain a ferroferric oxide/carbon polyhedral micro-nano multistage structure with high specific surface area, and the composite material obviously improves the specific capacitance and cycle life (2 Ag in 2 Ag) of an iron oxide-based supercapacitor-1After 3000 cycles at the current density of (1), the specific capacitance still remains 571.7F g-1And the specific capacitance retention rate is more than 88.8 percent), so that no relevant report is found at present.
The technical problem to be solved by the invention is to provide Fe3O4Application of the/C polyhedral material. The material is used for an electrode material of a super capacitor, has larger specific surface area and good rate performance and stability, and is suitable for high-power charge and discharge.
The invention finally solves the technical problem of providing a super capacitor adopting the composite material.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme: porous Fe3O4a/C polyhedral material, characterized in that the porous Fe3O4X-ray diffraction principal data for/C polyhedral material: 18.99 +/-0.5 degree, 31.2 +/-0.5 degree, 36.8 +/-0.5 degree, 38.5 +/-0.5 degree, 44.8 +/-0.5 degree, 55.6 +/-0.5 degree, 59.3 +/-0.5 degree, and 65.2 +/-0.5 degree3O4Characteristic peak of (1), corresponding to d spacing of
4.67 plus or minus 0.1, 2.86 plus or minus 0.1, 2.44 plus or minus 0.1, 2.34 plus or minus 0.1, 2.02 plus or minus 0.1, 1.65 plus or minus 0.1, 1.58 plus or minus 0.1 and 1.43 plus or minus 0.1, and the relative intensity% corresponding to the position of the above-mentioned appeared peak is 12.9 plus or minus 0.5, 31.9 plus or minus 0.5, 100.0, 9.3 plus or minus 0.5, 23.8 plus or minus 0.5, 10.7 plus or minus 0.5, 31.6 plus or minus 0.5 and 34.9 plus or minus 0.5. It is noted that a characteristic peak fluctuating into amorphous carbon appears at 23.5 ± 0.5 °.
Wherein, the porous Fe3O4the/C polyhedral material is in a micro-nano multilevel structure.
Wherein, the porous Fe3O4the/C polyhedral material is porous Fe3O4Specific surface area of 123.32m of/C polyhedral material2g-1～547.51m2g-1。
Wherein, the porous Fe3O4The element ratio of Fe to O to C of the/C polyhedral material is 1-1.5: 2: 1.
The invention also comprises said porous Fe3O4The preparation method of the/C polyhedral material comprises the following steps:
1) addition of polyhedral carbon to a catalyst containing Fe (CH)3COO)2And thiourea in water, carrying out hydrothermal reaction on the obtained mixture at 80-90 ℃ for 9-12 h to obtain Fe2O3Drying the/C composite material for later use;
2) fe obtained in the step 1)2O3And (3) insulating the/C composite material in the air at 400-500 ℃ for 2-4h, and cooling to obtain the composite material.
Wherein the polyhedral carbon is prepared by the following method: calcining the ZIF-67 polyhedron for 3-4 h at 700-800 ℃ under nitrogen to obtain a Co/C polyhedron, and then washing with 4-12M hydrochloric acid until Co ions are completely removed to obtain the catalyst.
Wherein, the specific conditions of the hydrochloric acid washing are as follows: stirring for 2h at 25-30 ℃, repeating for 5-8 times, washing with water to neutrality, and drying to obtain the final product.
Wherein the mass ratio of the Co/C polyhedron to the hydrochloric acid is 1: 1000, and the drying temperature is 80 ℃.
Wherein Fe (CH) in the step 1)3COO)2The mass ratio of thiourea to water is 1-2: 2-4: 100.
The invention also includes said porous Fe3O4The application of the/C polyhedral material in preparing the electrode material of the super capacitor.
The invention also comprises a super-capacitor electrode material which comprises the porous Fe3O4a/C polyhedral material.
Wherein, the super capacitor electrode material is 2Ag-1The specific capacity of 307.3-571.7 Fg is cycled for 3000 times under the current density-1。
Has the advantages that: compared with the prior art, the invention has the following advantages: the porous ferroferric oxide/carbon polyhedral supercapacitor electrode material is of a micron-nanometer multistage structure and has a large specific surface area (547.51 m)2g-1) Can provide more surface active sites. The composition of the ferroferric oxide and the carbon material can play a synergistic effect between the ferroferric oxide and the carbon material, namely, the good conductivity of the carbon material and the electric double layer effect between the materials are utilized to provide a stable electronic channel for the redox pseudocapacitance behavior of the ferroferric oxide, so that the ferroferric oxide can realize high specific capacity to the maximum extent under the high current density. The composite electrode can obtain higher discharge voltage, and the energy density and the power density of the electrode material are integrally improved.
Drawings
FIG. 1 carbon polyhedra and porous Fe obtained in example 13O4A Scanning Electron Microscopy (SEM) of the/C polyhedron;
FIG. 2 carbon polyhedra and porous Fe obtained in example 13O4Transmission Electron Microscopy (TEM) of the/C polyhedron;
FIG. 3 carbon polyhedra and porous Fe obtained in example 13O4X-ray diffraction pattern (XRD) of/C polyhedra wherein a is a carbon polyhedron and b is porous Fe3O4a/C polyhedral material;
FIG. 4 at Current Density 2Ag-1Porous Fe3O4Charge-discharge cycle diagram of/C polyhedral material.
Detailed Description
The present invention is further described below with reference to specific examples to enable those skilled in the art to better understand the present invention, but is not limited to the following examples.
The synthesis step of the ZIF-67 polyhedron in the embodiment of the invention comprises the following steps: 249.0mg Co (NO) was weighed out3)2·6H2O and 328.0mg of 2-methylimidazole were dissolved in 25.0mL of methanol, respectively. Next, the latter 2-methylimidazole methanol solution was slowly added to the former pink cobalt nitrate hexahydrate methanol solution to obtain a mixture, andthe mixture was sonicated at room temperature for 10 minutes to give a solution. The solution was then mixed and left to stand for 24 hours and the precipitate was collected by centrifugation, washed several times with methanol, and vacuum-dried at 80 ℃ for 24 hours to give ZIF-67 polyhedra.
Example 1 porous Fe3O4Preparation of/C polyhedra
The 400mg ZIF-67 polyhedron was placed in a quartz boat and placed in a tube furnace. Placing the tube furnace at 3 deg.C for min-1Heating to 700 ℃, annealing for 4 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain Co/C. Placing the obtained Co/C at 4mol L-1And (4) washing off metallic cobalt in HCl for 12 hours to obtain polyhedral carbon.
30mL of 50mmol was prepared. L is-1Fe(CH3COO)2Then 60mg of polyhedral carbon is added into the aqueous solution, ultrasonic treatment is carried out for 0.5h, and then magnetic stirring is carried out for 0.5h to obtain dispersion liquid. Adding 0.5g thiourea into the above dispersion, stirring for 0.5 hr, heating in 90 deg.C water bath for 12 hr, and centrifuging to obtain Fe2O3and/C, drying the precursor for 10 hours at 80 ℃. Drying the Fe2O3the/C precursor is put into a quartz boat and placed in a tube furnace. The tube furnace was heated to 500 ℃ and kept under air atmosphere for 4h (ramp rate 1 ℃ C. for min)-1) Removal of Fe2O3C and naturally cooling to room temperature to obtain porous Fe3O4a/C polyhedron having a specific surface area of 547.51m2g-1。
Example 2 porous Fe3O4Preparation of/C polyhedra
The 400mg ZIF-67 polyhedron was placed in a quartz boat and placed in a tube furnace. Placing the tube furnace at 3 deg.C for min-1Heating to 700 ℃, annealing for 4 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain Co/C. Placing the obtained Co/C at 4mol L-1And (4) washing off metallic cobalt in HCl for 12 hours to obtain polyhedral carbon.
The solution was 30mL of 25 mmol/L-1Fe(CH3COO)2Adding 30mg of polyhedral carbon into the aqueous solution, firstly carrying out ultrasonic treatment for 0.5h, and then carrying out magnetic stirring for 0.5h to obtain the productTo a dispersion. Adding 0.25g of thiourea into the dispersion, stirring for 0.5h, heating in a water bath at 90 deg.C for 12h, and centrifuging to obtain Fe2O3and/C, drying the precursor for 10 hours at 80 ℃. Fe to be dried2O3the/C precursor is put into a quartz boat and placed in a tube furnace. The tube furnace was heated to 500 ℃ and kept under air atmosphere for 4h (ramp rate 1 ℃ C. for min)-1) Removal of Fe2O3C and naturally cooling to room temperature to obtain porous Fe3O4a/C polyhedron.
Example 3 porous Fe3O4Preparation of/C polyhedra
The 400mg ZIF-67 polyhedron was placed in a quartz boat and placed in a tube furnace. Placing the tube furnace at 3 deg.C for min-1Heating to 700 ℃, annealing for 4 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain Co/C. Placing the obtained Co/C at 4mol L-1And (4) washing off metallic cobalt in HCl for 12 hours to obtain polyhedral carbon.
50mL of 100 mmol/L was placed-1Fe(CH3COO)2Then 120mg of polyhedral carbon is added into the aqueous solution, ultrasonic treatment is carried out for 0.5h, and then magnetic stirring is carried out for 0.5h to obtain dispersion liquid. Adding 1.0g of thiourea into the dispersion, stirring for 0.5h, heating in a water bath at 90 deg.C for 12h, and centrifuging to obtain Fe2O3and/C, drying the precursor for 10 hours at 80 ℃. The obtained Fe2O3the/C precursor is put into a quartz boat and placed in a tube furnace. The tube furnace was heated to 500 ℃ and kept under air atmosphere for 4h (ramp rate 1 ℃ C. for min)-1) Removal of Fe2O3C and naturally cooling to room temperature to obtain porous Fe3O4a/C polyhedron.
Example 4 porous Fe3O4Preparation of/C polyhedra
The 400mg ZIF-67 polyhedron was placed in a quartz boat and placed in a tube furnace. Placing the tube furnace at 1 deg.C for min-1Heating to 700 ℃, annealing for 4 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain Co/C. Placing the obtained Co/C at 4mol L-1Washing off gold in HCl for 12 hoursBelongs to cobalt, and finally obtains polyhedral carbon.
The amount of the catalyst was 30mL, 50 mmol. multidot.L-1Fe(CH3COO)2Then 60mg of polyhedral carbon is added into the aqueous solution, ultrasonic treatment is carried out for 0.5h, and then magnetic stirring is carried out for 0.5h to obtain dispersion liquid. Adding 0.5g thiourea into the above dispersion, stirring for 0.5 hr, heating in 90 deg.C water bath for 12 hr, and centrifuging to obtain Fe2O3and/C, drying the precursor for 10 hours at 80 ℃. The obtained Fe2O3the/C precursor is put into a quartz boat and placed in a tube furnace. The tube furnace was heated to 400 ℃ and kept under air atmosphere for 4h (ramp rate 1 ℃ C. for min)-1) Removal of Fe2O3C and naturally cooling to room temperature to obtain porous Fe3O4a/C polyhedron.
Example 5 porous Fe3O4Preparation of/C polyhedra
The 400mg ZIF-67 polyhedron was placed in a quartz boat and placed in a tube furnace. Placing the tube furnace at 3 deg.C for min-1Heating to 700 ℃, annealing for 4 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain Co/C. Placing the obtained Co/C at 4mol L-1And (4) washing off metallic cobalt in HCl for 12 hours to obtain polyhedral carbon.
50mL of 50 mmol. multidot.L was placed-1Fe(CH3COO)2Then 60mg of polyhedral carbon is added into the aqueous solution, ultrasonic treatment is carried out for 0.5h, and then magnetic stirring is carried out for 0.5h to obtain dispersion liquid. Adding 0.5g thiourea into the above dispersion, stirring for 0.5 hr, heating in 90 deg.C water bath for 12 hr, and centrifuging to obtain Fe2O3and/C, drying the precursor for 10 hours at the temperature of 60 ℃. The obtained Fe2O3the/C precursor is put into a quartz boat and placed in a tube furnace. The tube furnace was heated to 500 ℃ and kept under air atmosphere for 4h (ramp rate 1 ℃ C. for min)-1) Removal of Fe2O3C and naturally cooling to room temperature to obtain porous Fe3O4a/C polyhedron.
Example 6 porous Fe3O4Preparation of/C polyhedra
Placing 400mg ZIF-67 polyhedron intoThe quartz boat was placed in a tube furnace. Placing the tube furnace at 3 deg.C for min-1Heating to 700 ℃, annealing for 4 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain Co/C. Placing the obtained Co/C at 4mol L-1And (4) washing off metallic cobalt in HCl for 12 hours to obtain polyhedral carbon.
The arrangement was 50 mmol. multidot.L-1Fe(CH3COO)2Then 60mg of polyhedral carbon is added into the aqueous solution, ultrasonic treatment is carried out for 0.5h, and then magnetic stirring is carried out for 0.5h to obtain dispersion liquid. Adding 0.5g thiourea into the above dispersion, stirring for 0.5 hr, heating in 90 deg.C water bath for 10 hr, and centrifuging to obtain Fe2O3and/C, drying the precursor for 10 hours at 80 ℃. The obtained Fe2O3the/C precursor is put into a quartz boat and placed in a tube furnace. The tube furnace was heated to 500 ℃ and kept under air atmosphere for 4h (ramp rate 1 ℃ C. for min)-1) Removal of Fe2O3C and naturally cooling to room temperature to obtain porous Fe3O4a/C polyhedron having a specific surface area of 123.32m2g-1。
Example 7 preparation of supercapacitor electrode Material
The porous Fe particles of examples 1 to 6 were each prepared by using acetylene black as a conductive agent and polyvinylidene fluoride (PVDF) as a binder3O4Mixing the/C polyhedral active material, acetylene black conductive agent and polyvinylidene fluoride (PVDF) binder at a mass ratio of 8: 1, adding 200 μ L N-methyl pyrrolidone as solvent, ultrasonic treating in an ultrasonic machine for 6-8 hr, and coating on treated foam nickel (1 × 1 cm)2) And (3) putting the foamed nickel loaded with the active substance into a vacuum drying oven at 120 ℃ for drying to remove the solvent, and finally tabletting under the pressure of 10MPa to obtain the working electrode.
Experimental example Performance testing of electrode Material for supercapacitor
The porous Fe prepared in example 7 was loaded on the porous Fe of examples 1-63O4And performing related performance test on the supercapacitor in a 3.0M KOH solution by using/C polyhedral foamed nickel as a working electrode, a platinum sheet as a counter electrode and Hg/HgO as a reference electrode.
FIG. 1 shows porous Fe of examples 1 to 63O4the/C polyhedron basically keeps the shape of the carbon polyhedron template, the prepared composite material has rough surface, the rough surface can increase the surface area, and more active sites are provided for electrochemical redox reaction.
FIG. 2 shows porous Fe particles of examples 1 to 63O4the/C polyhedrons consist of small particles of 20nm and have a micro-porous structure. The porous structure is beneficial to the infiltration of electrolyte and the transmission of ions, and further promotes the kinetics of electrochemical reaction.
FIG. 3 shows porous Fe particles of examples 1 to 63O4XRD diffraction peak and Fe of/C polyhedron3O4The diffraction peak positions of the standard card PDFs (#26-1136) are consistent, and the fluctuation at about 25 ℃ is the characteristic peak of amorphous carbon.
From FIG. 4, it can be seen that example 1 is porous Fe3O4The electrode material of the/C polyhedron serving as the super capacitor is 2Ag-1The specific capacity of the lithium ion battery can still be maintained at 571.7F g after 3000 times of charge-discharge cycles under the current density-1Showing that the electrode has higher energy density and better cycle performance; and porous Fe synthesized in examples 2 to 63O4The specific capacitance of the material with/C polyhedron as the super capacitor is 319.6F g respectively after 3000 times of charge-discharge cycles-1，403.1F g-1，418.8F g-1，428.9F g-1，307.3F g-1The specific capacitance was lower than that in example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. Porous Fe3O4a/C polyhedral material, characterized in that said porous Fe3O4The X-ray diffraction data for the/C polyhedral material is: 18.99 +/-0.5 degrees, 31.2 +/-0.5 degrees, 36.8 +/-0.5 degrees, 38.5 +/-0.5 degrees, 44.8 +/-0.5 degrees, 55.6 +/-0.5 degrees and 59.3 +/-0 degrees.Fe appears at 5 degrees, 65.2 +/-0.5 degrees3O4The corresponding d spacing is A: 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, 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, and the porous Fe3O4the/C polyhedral material is of a micro-nano multilevel structure, and the porous Fe3O4Specific surface area of 123.32m for/C polyhedral material2 g-1~ 547.51 m2 g-1Said porous Fe3O4the/C polyhedral material is characterized in that the element ratio of Fe to O to C is = 1-1.5: 2: 1; the porous Fe3O4The preparation method of the/C polyhedral material comprises the following steps:
1) addition of polyhedral carbon to a catalyst containing Fe (CH)3COO)2And thiourea in water, carrying out hydrothermal reaction on the obtained mixture at 80-90 ℃ for 9-12 h to obtain Fe2O3Drying the/C composite material for later use;
2) fe obtained in the step 1)2O3And (3) insulating the/C composite material in air at 400-500 ℃ for 2-4h, and cooling to obtain the composite material.
2. Porous Fe of claim 13O4The preparation method of the/C polyhedral material is characterized by comprising the following steps of:
1) addition of polyhedral carbon to a catalyst containing Fe (CH)3COO)2And thiourea in water, carrying out hydrothermal reaction on the obtained mixture at 80-90 ℃ for 9-12 h to obtain Fe2O3Drying the/C composite material for later use;
2) fe obtained in the step 1)2O3And (3) insulating the/C composite material in air at 400-500 ℃ for 2-4h, and cooling to obtain the composite material.
3. Porous Fe according to claim 23O4The preparation method of the/C polyhedral material is characterized in that the polyhedral carbon is prepared by the following steps: calcining the ZIF-67 polyhedron for 3-4 h at 700-800 ℃ under nitrogen,and then, pickling with 4-12M hydrochloric acid until Co ions are completely removed.
4. Porous Fe according to claim 23O4The preparation method of the/C polyhedral material is characterized in that Fe (CH) in the step 1)3COO)2: thiourea: the mass ratio of water is 1-2: 2-4: 100.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271431A (en) * | 2015-10-12 | 2016-01-27 | 南京大学 | Method for preparing ferriferrous oxide magnetic material and composite material thereof |
| CN107731557A (en) * | 2017-08-23 | 2018-02-23 | 温州大学 | The preparation method and applications of electrode for super capacitor nitrogen oxygen codope porous carbon/ferriferrous oxide composite material |
| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN109473651A (en) * | 2018-11-09 | 2019-03-15 | 扬州大学 | By ZIF-67 derivative compounds metal sulfide Co in pairs8FeS8The method of/N-C polyhedron nano material |
| CN109494038A (en) * | 2018-11-06 | 2019-03-19 | 同济大学 | Ferroso-ferric oxide-nanoporous carbon nano-composite material and the preparation method and application thereof |
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|---|---|---|---|---|
| GB2502577A (en) * | 2012-05-31 | 2013-12-04 | Univ Dublin | Microparticles and a device and method for the production thereof |
-
2019
- 2019-06-21 CN CN201910546562.9A patent/CN110164703B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271431A (en) * | 2015-10-12 | 2016-01-27 | 南京大学 | Method for preparing ferriferrous oxide magnetic material and composite material thereof |
| CN107731557A (en) * | 2017-08-23 | 2018-02-23 | 温州大学 | The preparation method and applications of electrode for super capacitor nitrogen oxygen codope porous carbon/ferriferrous oxide composite material |
| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN109494038A (en) * | 2018-11-06 | 2019-03-19 | 同济大学 | Ferroso-ferric oxide-nanoporous carbon nano-composite material and the preparation method and application thereof |
| CN109473651A (en) * | 2018-11-09 | 2019-03-15 | 扬州大学 | By ZIF-67 derivative compounds metal sulfide Co in pairs8FeS8The method of/N-C polyhedron nano material |
Non-Patent Citations (2)
| Title |
|---|
| Fabrication and electrochemical properties of a graphene-enhanced hierarchical porous network of Fe3O4/carbon nanobelts;Xing Yu etc;《Electrochimica Acta》;20170724;第248卷;全文 * |
| Study of the Capacitive Behavior of MOF-Derived Nanocarbon Polyhedra;Uday Pratap Azad etc;《ChemistrySelect》;20181231;第3卷;第6107页右栏第1段，图3 * |
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