CN110033951A - The composite material and preparation method of a kind of oxide@sulfide core-shell structure and application - Google Patents
The composite material and preparation method of a kind of oxide@sulfide core-shell structure and application Download PDFInfo
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- CN110033951A CN110033951A CN201910289488.7A CN201910289488A CN110033951A CN 110033951 A CN110033951 A CN 110033951A CN 201910289488 A CN201910289488 A CN 201910289488A CN 110033951 A CN110033951 A CN 110033951A
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- nanometer rods
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000011258 core-shell material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910005809 NiMoO4 Inorganic materials 0.000 claims abstract description 56
- 239000002135 nanosheet Substances 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 12
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000002073 nanorod Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 238000004146 energy storage Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 229910015667 MoO4 Inorganic materials 0.000 claims description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000004378 air conditioning Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 238000010295 mobile communication Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 16
- 230000005611 electricity Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- -1 FeCo2O4 Chemical class 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical group [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018864 CoMoO4 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010408 sweeping 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Present disclose provides a kind of composite material of oxide@sulfide core-shell structure and preparation method and application, NiMoS4Nanoscale twins are attached to NiMoO4Nanorod surfaces are formed with NiMoO4Nanometer rods are core, with NiMoS4Nanometer sheet is the NiMoO of shell4Nanometer rods@NiMoS4The composite material of nanometer sheet.Its preparation process is, by NiMoO4Nanometer rods and sulphur source carry out sulfide modifier by hydro-thermal method and obtain NiMoO4Nanometer rods@NiMoS4Nanosheet composite material.The disclosure plays the synergistic effect of the two, to obtain the electrode material with higher performance by the combination of Oxide and sulfide.
Description
Technical field
The disclosure belongs to super capacitor manufacturing field, and in particular to a kind of composite wood of oxide@sulfide core-shell structure
Material and preparation method and application.
Background technique
Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.
Nowadays, energy crisis and environmental pollution become the huge problem for restricting human social development, development and utilization cleaning, ring
Protect, efficient new energy, such as solar energy, wind energy, tide energy be solve the problems, such as this must the road Hang Zhi.In view of major part can
In terms of the renewable sources of energy all have the defects that duration and generality, then energy conversion and storage device are become for new energy skill
The most important thing of art research.Have many advantages, such as that power density is high, have extended cycle life, charge/discharge speed is fast, no pollution to the environment, surpass
Grade capacitor has as a kind of new type of energy storage device in fields such as hybrid-power electric vehicle, pulse power system and emergency power supplies
Have wide practical use.
Electrode material for supercapacitor mainly has carbon-based material, metal-oxide based material and conducting polymer base
Material.Wherein, metal-oxide based material has very high theoretical specific capacity, and resourceful, low in cost, is studied
The very big concern of persons.In being studied known to the disclosed invention people at present, binary metal oxide, such as FeCo2O4、NiCo2O4、
CoMoO4And NiMoO4When Deng having preferable performance, but they are used alone as electrode material, low conductivity, which becomes, limits it
One huge problem of production application.
Summary of the invention
In order to solve the deficiencies in the prior art, purpose of this disclosure is to provide a kind of composite material of core-shell structure and preparations
Method and application play the synergistic effect of the two, to obtain having higher performance by the combination of Oxide and sulfide
Electrode material.
To achieve the goals above, the technical solution of the disclosure are as follows:
On the one hand, a kind of composite material of oxide@sulfide core-shell structure, NiMoS4Nanometer sheet is attached to NiMoO4It receives
Rice stick surface is formed with NiMoO4Nanometer rods are core, with NiMoS4Nanometer sheet is the NiMoO of shell4Nanometer rods@NiMoS4Nanometer sheet
Composite material.
Firstly, NiMoO4Nanorod structure can provide unobstructed electron propagation ducts, to reduce internal resistance；NiMoS4Nanometer
Lamella has biggish specific surface area, it is possible to provide reactivity site abundant and excellent electrolyte wellability, core-shell structure
It can be by NiMoO4Nanometer rods and NiMoS4Nanometer sheet combines, to obtain outstanding performance；Secondly, core-shell structure can also
So that NiMoO4Nanometer rods and NiMoS4Nanometer sheet is combined closely on molecular scale even atomic scale, to advanced optimize
The performance of composite material.
In order to find a kind of method for simply and efficiently preparing the combination electrode material, the application is based on existing simple
Hydrothermal synthesis method has successfully prepared the combination electrode material with high electrochemical performance.For this purpose, on the other hand the disclosure, mentions
The preparation method for having supplied a kind of composite material of core-shell structure, by NiMoO4Nanometer rods carry out vulcanization by hydro-thermal method with sulphur source and change
Property obtain NiMoO4Nanometer rods@NiMoS4Nanosheet composite material, the sulphur source are the inorganic matter containing sulfidion.
The composite material that the third aspect, a kind of above-mentioned composite material or above-mentioned preparation method obtain is in preparation supercapacitor
In application.
Fourth aspect, a kind of positive electrode, the composite material obtained including above-mentioned composite material or above-mentioned preparation method.
5th aspect, a kind of supercapacitor are made with the composite material that above-mentioned composite material or above-mentioned preparation method obtain
For the active material of positive electrode.
6th aspect, a kind of above-mentioned supercapacitor is in solar energy system, wind generator system, new energy vapour
Vehicle, intelligent distributed network system, distributed energy storage system, mobile communication base station, satellite communication system, radio communication system
System, City Rail Transit System, elevator, ventilating system, air-conditioning, supply and drain water system, aerospace equipment, electronic toy, mixing
Application in power electric motor car, pulse power system or emergency power supply.
The disclosure has the beneficial effect that
(1)NiMoS4Material has high conductivity and electrolyte wellability, NiMoO4Material has preferable stability, will
Two kinds of Material claddings can play the synergistic effect of the two, to obtain the electrode material with excellent chemical property.
(2) NiMoO has been prepared using simple hydrothermal synthesis method4Nano-bar material, and pass through step control vulcanization
Modification has obtained core-shell structure NiMoO4Nanometer rods@NiMoS4Nanosheet composite material realizes a step of ingredient and structure
Control.Disclosed method simple process, be easy to control, be low in cost, be suitble to industrialized production, prepare composite material it is high-efficient,
Stock utilization is high, has very excellent chemical property with the supercapacitor that the material makes.
(3) the core-shell structure NiMoO being prepared4Nanometer rods@NiMoS4Nanosheet composite material is by NiMoS4Nanometer sheet and
NiMoO4Nanometer rods composition；Wherein, NiMoS4Nanometer chip size is about 10-50nm, NiMoO4Nanorod diameter is about 50-
100nm, length are about 0.5-1 μm.Internal NiMoO4Nanometer rods can provide unobstructed electron propagation ducts, to reduce material
Internal resistance, external NiMoS4Nanometer sheet have biggish specific surface area and reactivity site abundant, be conducive to ion diffusion and
The generation of redox reaction.The material of both different scales is combined by core-shell structure, can further improve
The chemical property of composite material.
(4) core-shell structure NiMoO is used4Nanometer rods@NiMoS4The Asymmetric Supercapacitor tool of nanosheet composite material assembling
There are higher capacity, power density and energy density.
Detailed description of the invention
The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown
Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the disclosure.
Fig. 1 is the NiMoO of the embodiment of the present disclosure 14The scanning electron microscope (SEM) photograph of nano-bar material；
Fig. 2 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4The scanning electricity of nanosheet composite material
Mirror figure；
Fig. 3 is core-shell structure NiMoO prepared by the present embodiment4Nanometer rods@NiMoS4Nanosheet composite material and comparison
The made NiMoO of example 14The X-ray diffractogram of nanometer rods, wherein 1 is NiMoO4, 2 be NiMoO4@NiMoS4。
Fig. 4 is core-shell structure NiMoO prepared by the present embodiment4Nanometer rods@NiMoS4The energy disperse spectroscopy of nanosheet composite material
Spot scan picture.
Fig. 5 is core-shell structure NiMoO prepared by the present embodiment4Nanometer rods@NiMoS4The energy disperse spectroscopy of nanosheet composite material
Surface scan picture.
Fig. 6 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4The low power of nanosheet composite material is saturating
Penetrate electron microscope；
Fig. 7 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4The high power of nanosheet composite material is saturating
Penetrate electron microscope；
Fig. 8 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4Nanosheet composite material uses three electricity
CV (cyclic voltammetric) curve graph under different scanning rates is tested in pole；
Fig. 9 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4Nanosheet composite material uses three electricity
GCD (charge and discharge) curve graph under different current densities is tested in pole, wherein under the current density of 5A/g, capacity is
832.3F/g；
Figure 10 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4Nanosheet composite material and oxygen reduction
CV curve graph of the Asymmetric Supercapacitor that graphite alkene assembles under different scanning rates；
Figure 11 is the core-shell structure NiMoO of the embodiment of the present disclosure 14Nanometer rods@NiMoS4Nanosheet composite material and oxygen reduction
Charging and discharging curve figure of the Asymmetric Supercapacitor that graphite alkene assembles under different current densities, in the electricity of 0.5A/g
Under current density, capacity 73.1F/g；
Figure 12 is the NiMoO of disclosure comparative example 14Nano-bar material is using three electrode tests under different current densities
Charging and discharging curve figure, wherein under the current density of 5A/g, capacity 606.2F/g.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
The conductivity shown in view of binary metal oxide as energy storage device electrode material is low, it is difficult to meet practical raw
The deficiency of application is produced, in order to solve technical problem as above, the present disclosure proposes a kind of answering for oxide sulfide core-shell structure
Condensation material and preparation method and application.
A kind of exemplary embodiment of the disclosure provides a kind of composite material of oxide@sulfide core-shell structure,
NiMoS4Nanometer sheet is attached to NiMoO4Nanorod surfaces are formed with NiMoO4Nanometer rods are core, with NiMoS4Nanoscale twins are shell
NiMoO4Nanometer rods@NiMoS4The composite material of nanometer sheet.
Firstly, NiMoO4Nanorod structure can provide unobstructed electron propagation ducts, to reduce internal resistance；NiMoS4Nanometer
Piece has biggish specific surface area, it is possible to provide reactivity site abundant and excellent electrolyte wellability, core-shell structure can
By NiMoO4Nanometer rods and NiMoS4Nanometer sheet combines, to obtain outstanding performance；Secondly, core-shell structure can also be with
Make NiMoO4Nanometer rods and NiMoS4Nanometer sheet is combined closely on molecular scale even atomic scale, to advanced optimize multiple
The performance of condensation material.
In one or more embodiments of the embodiment, NiMoS4The size of nanometer sheet is 10~50nm.
In one or more embodiments of the embodiment, NiMoO4Nanorod diameter is 50~100nm, length 0.5
~1 μm.
In order to find a kind of method for simply and efficiently preparing the combination electrode material, the application is based on existing simple
Hydrothermal synthesis method has successfully prepared the combination electrode material with high electrochemical performance.The another embodiment of the disclosure,
A kind of preparation method of the composite material of core-shell structure is provided, by NiMoO4Nanometer rods are vulcanized with sulphur source by hydro-thermal method
It is modified to obtain NiMoO4Nanometer rods@NiMoS4Nanosheet composite material, the sulphur source are the inorganic matter containing sulfidion.
Inorganic matter containing sulfidion, such as vulcanized sodium, potassium sulfide etc..
In one or more embodiments of the embodiment, the concentration of sulphur source is 5 × 10 in the reaction system of sulfide modifier
-3~20 × 10-3mol/L。
The disclosure studies have shown that during sulfide modifier, different S2Concentration can have the structure of modified product
It directly affects, to influence the electric conductivity of material, mechanical property and chemical property.Therefore, the disclosure is by using difference
The sulphur source solution of concentration is tested, and has finally been determined during sulfide modifier under the concentration of the sulphur source, being capable of Effective Regulation
NiMoS4The growth of nanometer sheet, to obtain the composite material with good electric conductivity, mechanical stability and chemical property.
During sulfide modifier, the state of cure (vulcanization) and pattern of modified sample are generally difficult to control.The embodiment
In one or more embodiments, the hydro-thermal method condition of sulfide modifier is that temperature is 100~140 DEG C, and the reaction time is 6~12h.
It can get core-shell structure NiMoO under this condition4Nanometer rods@NiMoS4Nanosheet composite material, and the electric conductivity of composite material, power
It learns performance and chemical property significantly increases.
In one or more embodiments of the embodiment, NiMoO4Molar ratio with sulphur source is 1:5~20.
In one or more embodiments of the embodiment, the sulphur source is Na2S·9H2O。
In one or more embodiments of the embodiment of the disclosure, a kind of synthesis NiMoO is provided4The side of nanometer rods
Method carries out hydro-thermal reaction as raw material using nickel salt, molybdate and obtains NiMoO4Nanometer rods.
Nickel salt is the compound containing nickel ion, such as nickel nitrate, nickel sulfate in the disclosure.
Molybdate is the compound containing molybdenum acid ion, such as sodium molybdate, potassium molybdate in the disclosure.
Hydro-thermal method, the hydro-thermal reaction referred in the disclosure is to be carried out in closed pressure vessel using water as solvent
High temperature and pressure reaction.
In the series embodiment, in the nickel salt and molybdate, Ni2+、MoO4 2Molar ratio is 0.5~2:1.
In the series embodiment, the nickel salt is Ni (NO3)2·6H2O、NiCl2·6H2O or Ni (CH3COO)2·4H2O,
The molybdate is Na2MoO4·2H2O。
In hydrothermal system, the hydrolysis rate of temperature and metal salt has larger shadow to the formation of nucleus and the pattern of product
It rings.Therefore, in the series embodiment, the condition of hydro-thermal reaction is 120~180 DEG C of temperature, and the reaction time is 3~8h.The condition
The NiMoO of lower acquisition4Nanometer rods pattern is uniform, dispersed preferable.
In the series embodiment, Ni in the system of hydro-thermal reaction2+Concentration is 0.02~2mol/L, MoO4 2Concentration be
0.02~2mol/L.
The disclosure the third embodiment there is provided a kind of above-mentioned composite material or above-mentioned preparation method obtain it is compound
Application of the material in preparation supercapacitor.
Embodiment there is provided a kind of positive electrodes, including above-mentioned composite material or above-mentioned preparation for the 4th kind of the disclosure
The composite material that method obtains.
Embodiment there is provided a kind of supercapacitors for the 5th kind of the disclosure, with above-mentioned composite material or above-mentioned preparation
Active material of the composite material that method obtains as positive electrode.The supercapacitor is Asymmetric Supercapacitor.
In one or more embodiments of the embodiment, the preparation method of the electrode material of supercapacitor is to incite somebody to action
Active material and acetylene black, binder after mixing, are added solvent, nickel foam pole piece are applied to after mixing, dry.
In the series embodiment, binder is PVDF (Kynoar) bonding agent.
In the series embodiment, the mass ratio of active material, acetylene black and binder is 70~80:10~20:9~11.
In the series embodiment, drying condition is that 80~120 DEG C are dried in vacuo 10~16 hours.
In one or more embodiments of the embodiment, electrolyte is the KOH solution of 1~3mol/L.
In one or more embodiments of the embodiment, the active material of negative electrode material is redox graphene.
Pass through above-mentioned core-shell structure NiMoO4Nanometer rods@NiMoS4It is non-right that nanosheet composite material and redox graphene assemble
Supercapacitor is claimed to have many advantages, such as high capacity and power density, energy density.
Embodiment there is provided a kind of above-mentioned supercapacitors in solar energy system, wind for the 6th kind of the disclosure
Force generating system, new-energy automobile, intelligent distributed network system, distributed energy storage system, mobile communication base station, satellite communication
System, radio communications system, City Rail Transit System, elevator, ventilating system, air-conditioning, supply and drain water system, aerospace dress
Application in standby, electronic toy, hybrid-power electric vehicle, pulse power system or emergency power supply.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool
The technical solution of the disclosure is described in detail in the embodiment and comparative example of body.
Embodiment 1
One, core-shell structure NiMoO4Nanometer rods@NiMoS4The preparation of nanosheet composite material
Preparation step:
By 2mmol Ni (NO3)2·6H2O and 2mmol Na2MoO4·2H2O is dissolved in 60mL deionized water, uniform stirring
100mL reaction kettle is transferred to after 30 minutes, isothermal reaction 5 hours at 150 DEG C obtain NiMoO after washing is dry4Nano-bar
Material.
By 0.06mol Na2S·9H2O is dissolved in 60mL deionized water, after stirring and NiMoO4Nano-bar material is together
It pours into hydrothermal reaction kettle (100mL), 120 DEG C keep the temperature 8 hours, obtain core-shell structure NiMoO4Nanometer rods@NiMoS4Nanometer sheet is compound
Material.
Two, the preparation of Asymmetric Supercapacitor
With core-shell structure NiMoO4Nanometer rods@NiMoS4Nanosheet composite material is as active material, by active material, second
Acetylene black, PVDF bonding agent are mixed by the mass ratio of 8:1:1, and 1-Methyl-2-Pyrrolidone is added dropwise as solvent, applies after mixing evenly
Smear radius be 1.5cm nickel foam pole piece on, 100 DEG C vacuum drying 12 hours after respectively obtain positive and negative electrode material；It prepares
The KOH solution of 1mol/L, positive and negative electrode and test macro are connected, that is, are completed Asymmetric Supercapacitor.
Comparative example 1
It is same as Example 1, the difference is that: with NiMoO4Nano-bar material is as active material.
NiMoO4The preparation step of nano-bar material:
By 2mmol Ni (NO3)2·6H2O and 2mmol Na2MoO4·2H2O is dissolved in 60ml deionized water, uniform stirring
Reaction kettle is transferred to after 30 minutes, isothermal reaction 5 hours at 150 DEG C obtain NiMoO after washing is dry4Nano-bar material.
Embodiment 1 is characterized as below with comparative example 1.
NiMoO prepared by embodiment 14The scanning electron microscope analysis result of nanorod surfaces pattern is as shown in Figure 1.
The nanometer rods of any surface finish are arranged naturally, and single nanometer rods are having a size of 50~100nm.
Fig. 2 is core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4The scanning electricity of nanosheet composite material
Mirror picture, from Fig. 2 it can be found that vulcanization after nanometer rods outside by one layer of frivolous NiMoS4Nanoscale twins package, and receive
The dispersion in different angles of rice piece is arranged, and there are many gaps between lamella, to improve storage and the electronics, ion of electrolyte
Transmission speed.
Fig. 3 is core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4Nanosheet composite material and comparison
The made NiMoO of example 14The X-ray diffractogram of nanometer rods.As shown in figure 3, diffraction maximum in 1 diffraction image of comparative example can be with
Substance NiMoO4·xH2The standard diffraction card (JCPDS#13-0128) of O is corresponding, illustrates that obtained nanometer rods are NiMoO4At
Point.Diffraction maximum shape in embodiment diffraction image is also corresponding with standard card, illustrates that there is no generate newly in sulfidation
Substance.But as shown in illustration, the diffraction peak of 1 substance of embodiment is to offset at low angle, between the lattice for illustrating the substance
Away from increase, this is because the biggish S atom of atomic radius is instead of O atom.Therefore, the diffraction image illustrate in sulfidation at
Function has obtained NiMoS4Substance.
Fig. 4, Fig. 5 are core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4Nanosheet composite material is swept
Retouch Electronic Speculum spot scan and Surface scan picture.As can be seen that composite material outer layer is made of Ni, Mo, S element from spot scan Fig. 4,
In addition above-mentioned XRD diffraction patterns, therefore can determine that nanometer rods outer substance is NiMoS4.Fig. 5 is that first vegetarian noodles of composite material is swept
Retouch result, it can be seen that Ni, Mo, O, S element are uniformly distributed in selected rectangular area, illustrate that the composite material is removed containing NiMoS4
Also contain NiMoO outside substance4Ingredient.
Fig. 6, Fig. 7 are core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4Nanosheet composite material it is saturating
The sub- microscope photograph of radio.It it can be found that nanometer sheet and nanometer rods are closely chemical bonding from Fig. 6, and is polycrystalline structure.
The composite material of preparation, by NiMoS4Nanometer sheet and NiMoO4Nanometer rods composition, the NiMoS4Nanometer sheet is grown in NiMoO4It receives
Rice stick outer layer, size is about 10~50nm, the NiMoO4Nanorod diameter is about 50~100nm, and length is about 0.5~1 μm.
By the lattice fringe in Fig. 7, the spacing of lattice that can measure embodiment material is 0.326nm, the value and standard diffraction card
(JCPDS#13-0128) the peak institute at 27.334 ° is consistent to interplanar distance, illustrate the atomic arrangement of the material internal with
NiMoO4Substance is consistent, thus illustrates that material internal structure is still NiMoO4Substance.
In summary characterization result it can be concluded that, core-shell structure obtained by embodiment 1 is by internal NiMoO4Nanometer rods
With external NiMoS4Nanoscale twins composition.
Fig. 8 is core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4Nanosheet composite material uses three electricity
CV (cyclic voltammetric) curve graph under different scanning rates is tested in pole, according to line shapes in Fig. 8 and apparent redox
The appearance at peak, it can be seen that the material belongs to fake capacitance material, sweep speed is respectively 5,10,20,40mV/s in Fig. 8, with sweeping
The increase of rate is retouched, the area of CV curve is gradually increased, and oxidation, reduction peak occurs in 0.4V and 0.1V or so, with scanning
The increase of rate, peak position are deviated to the two poles of the earth respectively, illustrate that the material has preferable invertibity.
Fig. 9 is core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4Nanosheet composite material uses three electricity
The charging and discharging curve figure under different current densities is tested in pole, and current density is 5~15A/g, it can be seen in figure 9 that charge and discharge
Electric curve corresponds respectively to oxidation, the reduction peak of CV curve there are two platforms, and curve does not have apparent pressure drop, especially
Under low current density, illustrate that the material has preferable electric conductivity, under the current density of 5A/g, capacity 832.3F/
g。
Figure 10 is core-shell structure NiMoO prepared by embodiment 14Nanometer rods@NiMoS4Nanosheet composite material and oxygen reduction
CV curve graph of the Asymmetric Supercapacitor that graphite alkene assembles under different scanning rates, can be obtained, curve by Figure 10
Consist of two parts, within the scope of 0~0.5V, curve shows as class rectangle shape, this is typical electric double layer capacitance curve, says
The capacity source of the bright part is redox graphene material；Within the scope of 0.5~1.5V, figure line shows similar with Fig. 8
Shape, illustrate the voltage range inner capacities source be core-shell structure NiMoO4Nanometer rods@NiMoS4Nanosheet composite material.
By capacitative materials (redox graphene) and cell performance material (core-shell structure NiMoO4Nanometer rods@NiMoS4Nanometer sheet is compound
Material) combine, capacitor can be made while obtaining higher energy density and power density, this is also asymmetric super capacitor
The reason of device shows higher performance relative to other capacitors.
Figure 11 is core-shell structure NiMoO prepared by the present embodiment4Nanometer rods@NiMoS4Nanosheet composite material and reduction
Discharge curve of the Asymmetric Supercapacitor that graphene oxide assembles under different current densities, in the electricity of 0.5A/g
Under current density, capacity 73.4F/g, when current density increases to 5A/g, capacity 34.8F/g illustrates the composite material group
The Asymmetric Supercapacitor dressed up has preferable high rate performance.
Figure 12 is NiMoO prepared by comparative example 14Nano-bar material uses the corresponding resulting charge and discharge of three electrode tests
The performance test results, under the current density of 5A/g, capacity 606.2F/g.It can be seen that the core-shell structure of embodiment 1
NiMoO4Nanometer rods@NiMoS4Nanosheet composite material will be significantly better than the NiMoO of comparative example 1 on capacity and high rate performance4It receives
Rice bar material.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field
For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair
Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.
Claims (10)
1. a kind of composite material of oxide@sulfide core-shell structure, characterized in that NiMoS4Nanometer sheet is attached to NiMoO4It receives
Rice stick surface is formed with NiMoO4Nanometer rods are core, with NiMoS4Nanoscale twins are the NiMoO of shell4Nanometer rods@NiMoS4Nanometer sheet
Composite material.
2. composite material as described in claim 1, characterized in that NiMoS4The size of nanometer sheet is 10~50nm；
Or, NiMoO4Nanorod diameter is 50~100nm, and length is 0.5~1 μm.
3. a kind of preparation method of the composite material of core-shell structure, characterized in that by NiMoO4Nanometer rods and sulphur source pass through hydro-thermal method
It carries out sulfide modifier and obtains NiMoO4Nanometer rods@NiMoS4Nanosheet composite material, the sulphur source are the nothing containing sulfidion
Machine object.
4. preparation method as claimed in claim 3, characterized in that in the reaction system of sulfide modifier the concentration of sulphur source be 5 ×
10-3~20 × 10-3mol/L；
Or, the hydro-thermal method condition of sulfide modifier is, temperature is 100~140 DEG C, and the reaction time is 6~12h；
Or, NiMoO4Molar ratio with sulphur source is 1:5~20；
Or, the sulphur source is Na2S·9H2O。
5. preparation method as claimed in claim 3, characterized in that synthesis NiMoO4The method of nanometer rods, with nickel salt, molybdate
Hydro-thermal reaction, which is carried out, as raw material obtains NiMoO4Nanometer rods；
Preferably, in the nickel salt and molybdate, Ni2+、MoO4 2-Molar ratio is 0.5~2:1；
Preferably, the nickel salt is Ni (NO3)2·6H2O、NiCl2·6H2O or Ni (CH3COO)2·4H2O, the molybdate are
Na2MoO4·2H2O；
Preferably, the condition of hydro-thermal reaction is 120~180 DEG C of temperature, and the reaction time is 3~8h；
Preferably, Ni in the system of hydro-thermal reaction2+Concentration is 0.02~2mol/L, MoO4 2-Concentration be 0.02~2mol/L.
6. what a kind of composite material of any of claims 1 or 2 or any preparation method of claim 3~5 obtained answers
Application of the condensation material in preparation supercapacitor.
7. a kind of positive electrode, characterized in that any including composite material of any of claims 1 or 2 or claim 3~5
The composite material that the preparation method obtains.
8. a kind of supercapacitor, characterized in that any with composite material of any of claims 1 or 2 or claim 3~5
Active material of the composite material that the preparation method obtains as positive electrode.
9. supercapacitor as claimed in claim 8, characterized in that the preparation method of the electrode material of supercapacitor is,
After mixing by active material and acetylene black, binder, solvent is added, nickel foam pole piece is applied to after mixing, dries；
Preferably, binder is PVDF bonding agent；
Preferably, the mass ratio of active material, acetylene black and binder is 70~80:10~20:9~11；
Preferably, drying condition is that 80~120 DEG C are dried in vacuo 10~16 hours；
Or, electrolyte is the KOH solution of 1~3mol/L；
Or, the active material of negative electrode material is redox graphene.
10. supercapacitor described in a kind of claim 8 or 9 is in solar energy system, wind generator system, new energy vapour
Vehicle, intelligent distributed network system, distributed energy storage system, mobile communication base station, satellite communication system, radio communication system
System, City Rail Transit System, elevator, ventilating system, air-conditioning, supply and drain water system, aerospace equipment, electronic toy, mixing
Application in power electric motor car, pulse power system or emergency power supply.
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| CN112490019A (en) * | 2020-12-09 | 2021-03-12 | 桂林电子科技大学 | Polydopamine-coated MXene-based composite material and preparation method and application thereof |
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| CN110517894A (en) * | 2019-08-29 | 2019-11-29 | 武汉理工大学 | Based on cobalt acid lanthanum, the asymmetric capacitor of graphene oxide and preparation method thereof |
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