CN109659150A - The composite material of core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted - Google Patents
The composite material of core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted Download PDFInfo
- Publication number
- CN109659150A CN109659150A CN201910013674.8A CN201910013674A CN109659150A CN 109659150 A CN109659150 A CN 109659150A CN 201910013674 A CN201910013674 A CN 201910013674A CN 109659150 A CN109659150 A CN 109659150A
- Authority
- CN
- China
- Prior art keywords
- nickel foam
- grown
- core
- coo
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 55
- 239000006260 foam Substances 0.000 title claims abstract description 53
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 36
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000012924 metal-organic framework composite Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 239000002070 nanowire Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- H01G11/46—Metal oxides
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明涉及原位生长在泡沫镍上的过渡金属氧化物与金属有机骨架构成的核壳结构复合材料。制备方法包括：先制备生长在泡沫镍上的纳米线阵列自组装的花状CoO簇，然后制备生长在泡沫镍上的核壳结构的ZIF‑67@CoO，最后制备生长在泡沫镍上的核壳结构的Co/C‑N@CoO。与现有技术相比，本发明提供的制备方法产物纯度高、分散性好且可控制，工艺步骤简单，易于操作。所制得的核壳结构的过渡金属氧化物与金属有机骨架复合材料生长在泡沫镍基底上，可直接作为超级电容器的电极材料，具有优异的电容性能，可应用在高稳定性，可穿戴电子器件等场合。
The invention relates to a core-shell structure composite material composed of transition metal oxide and metal-organic framework grown on nickel foam in situ. The preparation method includes: firstly preparing a flower-like CoO cluster grown on the foamed nickel array self-assembled, then preparing the ZIF-67@CoO with a core-shell structure grown on the nickel foam, and finally preparing the core grown on the nickel foam Shell-structured Co/C‑N@CoO. Compared with the prior art, the preparation method provided by the present invention has the advantages of high product purity, good dispersibility and controllability, simple process steps and easy operation. The obtained core-shell structured transition metal oxide and metal-organic framework composites are grown on nickel foam substrates, which can be directly used as electrode materials for supercapacitors, with excellent capacitance properties, and can be applied in high-stability, wearable electronics devices, etc.
Description
Technical field
The invention belongs to materialogy fields, and specifically a kind of nano-wire array of growth in situ in nickel foam is constituted
Flower-shaped transition metal oxide and the composite material and preparation method of core-shell structure that constitutes of metal organic framework and super
Application in grade capacitor.
Background technique
With the continuous development of portable electronic device, the research of power storage and release becomes countries nowadays scientist's
Research hotspot.Mobile electronic device is positive light, small, flexible, foldable or even wearable in order to meet user's demand
Trend development.Supercapacitor is by electrode, and the energy storage device of electrolyte and collector composition, is performance between battery and tradition
The novel energy-storing equipment of capacitor.Compared with traditional capacitor, with high power density, the charging time is short, have extended cycle life,
Advantages of environment protection, in the fields such as mobile communication, portable electronic device, new-energy automobile, aerospace and national defence table
Reveal broad application prospect.All the time, researchers, which are dedicated to preparation, there is mechanical robustness to have large energy again
The supercapacitor of density and power density.Fake capacitance capacitor based on transition metal oxide, due to theoretical specific capacitance is high,
The disadvantages of low and multiple oxidation state of preparation cost is the most potential material of pseudocapacitors, but electron-transporting is poor limited
The fake capacitance characteristic for crossing metal oxide causes capacitive property far below theoretical value.
Summary of the invention
For existing transition metal oxide there are a series of disadvantage such as electron conduction difference, the purpose of the present invention is mention
There is satisfactory electrical conductivity for one kind, high capacitance, high energy density and power density, self-supporting, bent flexibility are super
The preparation method of the combination electrode material of grade capacitor and flower-shaped core-shell structure.
The technical solution adopted by the present invention is that: transition metal oxide of the growth in situ in nickel foam and the organic bone of metal
The composite material of core-shell structure that frame is constituted, preparation method include the following steps:
1) it is grown in the preparation of the flower-shaped CoO cluster of the nano-wire array self assembly in nickel foam: by cobalt salt, urea and fluorination
Ammonia is add to deionized water, and is uniformly mixed to obtain mixed liquor, nickel foam is impregnated into mixed liquor, is then transferred to poly- four
It in vinyl fluoride autoclave, is put into baking oven after sealing, is warming up to 100-150 DEG C, reacted 5-15h, be slowly cooled to room temperature,
It after standing at least 1 day, filters, washs, it is dry；Products therefrom is transferred in tube furnace, is warming up to 300-400 DEG C, calcines 0.5-
1.5h, the CoO that must be grown in nickel foam.
Preferably, the cobalt salt is cobalt nitrate or cobalt acetate.
Preferably, after urea is add to deionized water, final concentration of 0.15mol/L.
Preferably, after ammonium fluoride is add to deionized water, final concentration of 0.1mol/L.
Preferably, it is put into baking oven after sealing, is warming up to 100 DEG C, react 10h.
Preferably, products therefrom is transferred in tube furnace, is warming up to 350 DEG C, calcines 1h.
Preferably, the heating rate of tube furnace is 4 DEG C of min-1, rate of temperature fall is 5 DEG C of min-1。
2) preparation of the ZIF-67@CoO for the core-shell structure being grown in nickel foam: nickel foam will be grown in obtained by step 1)
On CoO be placed in the mixed solution of second alcohol and water of 2-methylimidazole, be placed in vial and seal, be stored at room temperature reaction 12-
72h is washed, dry, the ZIF-67@CoO that must be grown in nickel foam；
Preferably, it is placed in vial and seals, be stored at room temperature reaction for 24 hours.
3) preparation of the Co/C-N@CoO for the core-shell structure being grown in nickel foam: nickel foam will be grown in obtained by step 2)
On ZIF-67@CoO be transferred in porcelain boat, be placed in tube furnace, under inert gas shielding, be first warming up to 300-400 DEG C, forge
2-4h is burnt, it is further heated up to 500-600 DEG C, 1-3h is calcined, is down to room temperature, the Co/C-N@CoO that must be grown in nickel foam is multiple
Condensation material.
Preferably, it is placed in tube furnace, under inert gas shielding, is first warming up to 350 DEG C, calcines 3h, be further continued for heating up
To 500 DEG C, 2h is calcined.
Preferably, the heating rate of tube furnace is 4 DEG C of min-1, rate of temperature fall is 5 DEG C of min-1。
The core-shell structure that transition metal oxide of the above-mentioned growth in situ in nickel foam and metal organic framework are constituted
Application of the composite material as electrode material in supercapacitor.
The nucleocapsid knot that the transition metal oxide of growth in situ of the invention in nickel foam and metal organic framework are constituted
The preparation process flow of structure composite material are as follows: the flower-shaped CoO cluster for the nano-wire array self assembly being grown in nickel foam is first prepared,
Secondly the ZIF-67@CoO for preparing the core-shell structure being grown in nickel foam, finally prepares the core-shell structure being grown in nickel foam
Co/C-N@CoO.
The beneficial effects of the present invention are:
(1) of the invention, selecting transition metal oxide and metal-organic framework materials is raw material, using solvent-thermal method and heat
The composite material of solution preparation self-supporting.This method operation is easy, and equipment is simple, and preparation process is pollution-free.
(2) of the invention, since the transition metal oxide used is CoO, theory specific capacitance with higher, metal has
The porous structure of machine framework material itself and graphited C, N doping, are conducive to the accumulation of charge and the biography of electrolyte ion
It is defeated, be conducive to the raising of specific capacitance.
(3) of the invention, due to the nanowire array structure of the CoO of preparation itself, the transmission of electronics can be conducive to.
(4) of the invention, transition metal oxide and the metal organic framework composite material of synthesis can be used for flexible all solid state
Electrode material for super capacitor.
(5) present invention prepares transition metal oxide and metal organic framework composite wood using solvent-thermal method and pyrolysismethod
Material, processing step is simple, easily operated, and combination electrode material obtained has a high specific surface area, hierarchical porous structure, and its
With excellent capacitive property, high stability, the occasion of high power density power supply can be applicable to.
(6) compared with prior art, preparation method product purity height provided by the invention, good dispersion and controllable, work
Skill step is simple, easily operated.The transition metal oxide and metal organic framework composite material of obtained core-shell structure are raw
It grows in foam nickel base, can have excellent capacitive property directly as the electrode material of supercapacitor, can be applicable to height
Stability, the occasions such as wearable electronic device.
Detailed description of the invention
Fig. 1 is the nucleocapsid that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The XRD of structural composite material tests map.
Fig. 2 is the nucleocapsid that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The SEM and TEM of structural composite material scheme；
Wherein, a, d:CoO@Ni；b,e:ZIF-67@CoO@Ni；c,f:Co/C-N@CoO@Ni.
Fig. 3 is the nucleocapsid that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
EDS power spectrum after structural composite material pyrolysis.
Fig. 4 is the nucleocapsid that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The cyclic voltammetry curve of structural composite material.
Fig. 5 is the nucleocapsid that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The constant current charge-discharge curve of structural composite material.
Fig. 6 is the nucleocapsid that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The Nyquist diagram of the impedance behavior test of structural composite material.
Specific embodiment
Technical characterstic of the invention is illustrated below with reference to specific experiment scheme and attached drawing, but the present invention is not limited thereto.
Test method described in following example is unless otherwise specified conventional method；The instrument and material, unless otherwise specified,
Commercially obtain.
The core-shell structure that transition metal oxide of 1 growth in situ of embodiment in nickel foam and metal organic framework are constituted
The preparation of composite material (one) CoO@Ni:
By the cobalt nitrate of 0.05mmol, 0.3mmol urea, 0.2mmol ammonium fluoride is added in the deionized water of 2mL, is stirred
Uniformly mixed mixed liquor is mixed, by clean nickel foam (1 × 1.5cm2) be impregnated into mixed liquor, then by nickel foam and mixing
Liquid is transferred to jointly in the polytetrafluoroethylene (PTFE) autoclave that volume is 10mL.Reaction kettle is sealed and is put into baking oven.Heating
The temperature of baking oven is set to reach 100 DEG C from room temperature, heating rate is 2 DEG C of min-1, and it is small to maintain the temperature at heat preservation 10 under this condition
When.It is slowly cooled to room temperature, stands at least 1 day, obtain the nickel foam of dark red precipitate cladding；Water and ethyl alcohol are successively used in filtering
Washing, and dry 6h, products therefrom are transferred in tube furnace under the conditions of 60 DEG C in air, are warming up to 350 DEG C, are calcined 1h, obtain
The CoO being grown in nickel foam is as grown in the flower-shaped CoO cluster of the nano-wire array self assembly in nickel foam, is labeled as
CoO@Ni。
(2) preparation of ZIF-67@CoO@Ni:
The 2-methylimidazole of 10mmol is added in the mixed solution of the ethyl alcohol of 5mL and the water of 5mL, ultrasonic 10min is obtained
Reaction solution.CoO@Ni is impregnated into reaction solution, is transferred in the vial that volume is 25mL together.Vial is covered close
It seals, stands 24 hours at room temperature, obtain the nickel foam of purple precipitating cladding.Water and ethanol washing are successively used, and dry in vacuum
Drying 12h, the ZIF-67@CoO that must be grown in nickel foam under the conditions of 80 DEG C, is labeled as ZIF-67@CoO@Ni in dry case.
(3) preparation of Co/C-N@CoO@Ni:
ZIF-67@CoO@Ni is transferred in porcelain boat, is placed in tube furnace, under argon gas protection, is warming up to first
350 DEG C, heating rate is 4 DEG C of min-1, 3h is calcined, it is further heated up to 500 DEG C, heating rate is 4 DEG C of min-1, 2h is calcined,
It is down to room temperature, the Co/C-N@CoO composite material that must be grown in nickel foam is labeled as Co/C-N@CoO@Ni.
(4) it detects
1) performance indicator such as table 1
Table 1
| Material | Specific surface area (m2g-1) | Pore volume (cm3g-1) |
| CoO@Ni | 27.9 | 0.044 |
| ZIF-67@CoO@Ni | 520.7 | 0.229 |
| Co/C-N@CoO@Ni | 562.4 | 0.253 |
Seen from table 1, the flower-shaped CoO cluster that nano-wire array is constituted is compound with ZIF-67, constitutes the ZIF-67@of core-shell structure
CoO, annealed processing, specific surface area increase, and pore volume increases, and after illustrating compound ZIF-67, specific surface area is dramatically increased.
2) Fig. 1 is the core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted
The XRD diagram of composite material.As seen from Figure 1, the transition metal oxide of the core-shell structure in the present invention and metal organic framework are multiple
Condensation material is successfully prepared.
3) Fig. 2 is the core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted
The scanning electron microscope and transmission electron microscope photo (SEM and TEM) of composite material.From Figure 2 it can be seen that prepared by the present invention
The composite material for the core-shell structure that the flower-shaped transition metal oxide and metal organic framework that nano-wire array is constituted are constituted is presented
Core-shell structure.By Fig. 2 (a, d) as it can be seen that obtaining the flower-shaped CoO cluster of nano-wire array self assembly, the width of a CoO nano wire is about
15-20nm.By Fig. 2 (b, e) as it can be seen that ZIF-67 CoO is at core-shell structure, ZIF-67 particle has granatohedron pattern simultaneously
Homoepitaxial is in CoO nanowire surface.By Fig. 2 (c, f) as it can be seen that ZIF-67@CoO maintains intact nucleocapsid after high-temperature calcination
Structure, and ZIF-67 it is intact save granatohedron pattern.
4) Fig. 3 is the core that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
EDS power spectrum after core-shell structure composite material pyrolysis.It can be obtained by Fig. 3 analysis, the transiting metal oxidation of present invention gained core-shell structure
Composite material after object is pyrolyzed with metal organic framework is made of tetra- kinds of elements of C, N, O, Co.
5) Fig. 4 is the core that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The cyclic voltammetry curve of core-shell structure composite material.It can be obtained by Fig. 4 analysis, the transition metal oxide of present invention gained core-shell structure
With metal organic framework composite material in the case where difference sweeps speed, image current response is showed, and there are redox peaks, illustrate it
Not only there is electric double layer capacitance feature, but also there is fake capacitance feature.And in the case where difference sweeps speed, good cycle performance is shown.
6) Fig. 5 is that transition metal oxide and metal organic framework of a kind of growth in situ of the present invention in nickel foam are constituted
Composite material of core-shell structure constant current charge-discharge curve.It can be obtained by Fig. 5 analysis, present invention gained combination electrode material is in 2-
20mAcm-2Under current density, the isosceles triangle charging and discharging curve of distortion is shown, illustrates it with fake capacitance capacitive property.
And under different current densities, good high rate performance is shown.
7) Fig. 6 is the core that transition metal oxide of the growth in situ of the present invention in nickel foam and metal organic framework are constituted
The impedance of core-shell structure composite material can be tested.It will be appreciated from fig. 6 that transition metal oxide and metal organic framework composite material are pyrolyzed
Equal series resistance is reduced to 0.62 Ω by 1.42 Ω afterwards, illustrates that graphited C, N doping effectively improves combination electrode material
The electric conductivity of material.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910013674.8A CN109659150A (en) | 2019-01-08 | 2019-01-08 | The composite material of core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910013674.8A CN109659150A (en) | 2019-01-08 | 2019-01-08 | The composite material of core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109659150A true CN109659150A (en) | 2019-04-19 |
Family
ID=66119016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910013674.8A Pending CN109659150A (en) | 2019-01-08 | 2019-01-08 | The composite material of core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109659150A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280269A (en) * | 2019-07-19 | 2019-09-27 | 曲阜师范大学 | A kind of the cobalt-based petal-shaped composite material and preparation method and application of silver nano-grain load |
| CN110350205A (en) * | 2019-07-11 | 2019-10-18 | 四川大学 | Derivative metal nitride/the carbon composite of ZIFs and preparation method and purposes |
| CN111072690A (en) * | 2019-12-25 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | A kind of flower-shaped metal-organic framework composite material, its preparation method and application |
| CN111524714A (en) * | 2020-04-06 | 2020-08-11 | 电子科技大学 | A kind of preparation method of self-supporting nanoarray with secondary structure |
| CN112978870A (en) * | 2021-03-25 | 2021-06-18 | 辽宁大学 | MoO3-xPreparation method and application of/C/CoO nano composite material |
| CN114984934A (en) * | 2022-06-07 | 2022-09-02 | 大连理工大学 | Preparation method of foam metal in-situ growth MOFs (metal-organic frameworks) hierarchical pore composite material and application of foam metal in-situ growth MOFs hierarchical pore composite material in electro-adsorption of pollutants |
| CN117342536A (en) * | 2023-09-15 | 2024-01-05 | 碳一新能源集团有限责任公司 | Multi-mesoporous carbon material, silicon-carbon anode material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103632856A (en) * | 2013-12-03 | 2014-03-12 | 华中师范大学 | Production method and application of cobaltous oxide/carbon nanostructure array |
| CN107159297A (en) * | 2017-06-21 | 2017-09-15 | 黑龙江大学 | A kind of difunctional VPO catalysts cobalt/cobaltosic oxide/nitrogen carbon composite and preparation method thereof |
| CN108346522A (en) * | 2018-03-28 | 2018-07-31 | 安徽师范大学 | A kind of cobaltosic oxide hierarchical structure nano-array material, preparation method and applications |
-
2019
- 2019-01-08 CN CN201910013674.8A patent/CN109659150A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103632856A (en) * | 2013-12-03 | 2014-03-12 | 华中师范大学 | Production method and application of cobaltous oxide/carbon nanostructure array |
| CN107159297A (en) * | 2017-06-21 | 2017-09-15 | 黑龙江大学 | A kind of difunctional VPO catalysts cobalt/cobaltosic oxide/nitrogen carbon composite and preparation method thereof |
| CN108346522A (en) * | 2018-03-28 | 2018-07-31 | 安徽师范大学 | A kind of cobaltosic oxide hierarchical structure nano-array material, preparation method and applications |
Non-Patent Citations (2)
| Title |
|---|
| SHUHAI WANG等: "Nanoparticle Cookies Derived from Metal-Organic Frameworks: Controlled Synthesis and Application in Anode Materials for Lithium-Ion Batteries", 《SMALL》 * |
| SIMENG DAI等: "Metal–organic framework-templated synthesis of sulfur-doped core–sheath nanoarrays an nanoporous carbon for flexible all-solid-stat asymmetric supercapacitors", 《NANOSCALE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350205A (en) * | 2019-07-11 | 2019-10-18 | 四川大学 | Derivative metal nitride/the carbon composite of ZIFs and preparation method and purposes |
| CN110350205B (en) * | 2019-07-11 | 2021-12-28 | 四川大学 | ZIFs-derived metal nitride/carbon composite material, and preparation method and application thereof |
| CN110280269A (en) * | 2019-07-19 | 2019-09-27 | 曲阜师范大学 | A kind of the cobalt-based petal-shaped composite material and preparation method and application of silver nano-grain load |
| CN111072690A (en) * | 2019-12-25 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | A kind of flower-shaped metal-organic framework composite material, its preparation method and application |
| CN111524714A (en) * | 2020-04-06 | 2020-08-11 | 电子科技大学 | A kind of preparation method of self-supporting nanoarray with secondary structure |
| CN112978870A (en) * | 2021-03-25 | 2021-06-18 | 辽宁大学 | MoO3-xPreparation method and application of/C/CoO nano composite material |
| CN112978870B (en) * | 2021-03-25 | 2022-06-14 | 辽宁大学 | MoO3-xPreparation method and application of/C/CoO nano composite material |
| CN114984934A (en) * | 2022-06-07 | 2022-09-02 | 大连理工大学 | Preparation method of foam metal in-situ growth MOFs (metal-organic frameworks) hierarchical pore composite material and application of foam metal in-situ growth MOFs hierarchical pore composite material in electro-adsorption of pollutants |
| CN117342536A (en) * | 2023-09-15 | 2024-01-05 | 碳一新能源集团有限责任公司 | Multi-mesoporous carbon material, silicon-carbon anode material, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109659150A (en) | The composite material of core-shell structure that transition metal oxide of the growth in situ in nickel foam and metal organic framework are constituted | |
| CN104517739B (en) | Titania based electrode material for super capacitor and preparation method thereof | |
| CN108461306B (en) | A kind of multi-level N-doped carbon nanorod composite material and preparation method thereof | |
| CN107601580A (en) | A kind of method for preparing nickel cobalt oxide as presoma by the use of metal organic framework and application thereof | |
| CN110335759B (en) | Carbon nanofiber composites supported by nickel hydroxide and nickel cobaltate | |
| CN106315695A (en) | Strawberry like Ni-Co nano material and preparing method thereof | |
| CN108658119B (en) | Method and application for preparing copper sulfide nanosheets and their composites by low temperature vulcanization technology | |
| CN106410153B (en) | A kind of titanium nitride cladding nickel titanate composite material and preparation method and application | |
| CN112670093A (en) | Porous Co3O4@ Ni-MOF core-shell structure nanosheet array material and preparation method and application thereof | |
| CN107739023A (en) | A kind of polyhedron bimetallic oxide and its production and use | |
| CN109616331A (en) | A core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof | |
| CN107240505A (en) | Electrode material for super capacitor Zn doping NiCo2O4Compound and preparation method | |
| CN106654401A (en) | Bismuth ferrite/nickel hydroxide secondary alkali battery and preparation method therefor | |
| CN105810456B (en) | A kind of activated graphene/needle-like nickel hydroxide nano composite and preparation method thereof | |
| CN107633952A (en) | A kind of nickel manganese composite oxide nano sheet film materials and its preparation method and application | |
| CN110197769B (en) | A kind of composite carbon nanotube material and its preparation method and application | |
| CN106683896A (en) | Preparation method and application of core-shell-structured nickel molybdate/manganese dioxide composite material | |
| CN110310835A (en) | A kind of nano-flower-like NiS@NiCo2S4 micro-nano electrode material and its preparation method and application | |
| CN109216038B (en) | A flexible self-supporting ternary metal sulfide/carbon foam composite electrode material | |
| CN106006763A (en) | Method for preparing nickel cobaltate nanocrystalline assembly | |
| CN109671574B (en) | A kind of MnCo2O4 nanosphere particle and its preparation method and application in supercapacitor | |
| CN106328383B (en) | A kind of preparation method of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite material | |
| CN109243829A (en) | A dye-sensitized battery electrode and its preparation method and application of MIL-47 material | |
| CN108962617B (en) | Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere | |
| CN108682562B (en) | A kind of γ-Fe of C doping2O3Nanocomposite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190419 |