CN106277078A - A kind of hollow sub-microsphere with multilamellar nickel sulfide shell and its preparation method and application - Google Patents
A kind of hollow sub-microsphere with multilamellar nickel sulfide shell and its preparation method and application Download PDFInfo
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- CN106277078A CN106277078A CN201610679098.7A CN201610679098A CN106277078A CN 106277078 A CN106277078 A CN 106277078A CN 201610679098 A CN201610679098 A CN 201610679098A CN 106277078 A CN106277078 A CN 106277078A
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- multilamellar
- nickel
- microsphere
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- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000004005 microsphere Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 7
- 235000013877 carbamide Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of hollow sub-microsphere with multilamellar nickel sulfide shell and its preparation method and application, initially with the cryogenic fluid sedimentation method, nickel presoma is grown on carbon ball surface, calcining obtains the hollow sub-microsphere of multilamellar nickel oxide shell in atmosphere, and nickel oxide micron ball vulcanizes in tube furnace hollow sub-microsphere afterwards that obtain complete multilamellar nickel sulfide shell.The hollow-core construction of unique multilayer package not only contributes to effective infiltration of electrolyte, electrolyte and active substance can be made to be fully contacted simultaneously, thus improve the chemical property of material.The hollow nickel sulfide micron ball of multilayer package prepared by the present invention is used as electrode material for super capacitor and has good chemical property, and technique is simple, mild condition.
Description
Technical field
The present invention relates to a kind of hollow sub-microsphere with multilamellar nickel sulfide shell and preparation method thereof and at super capacitor
Application in device.
Background technology
Ultracapacitor has another name called electrochemical capacitor, is the electricity between traditional capacitor and battery with property
Source.Ultracapacitor have have extended cycle life, the charging interval is short, operating temperature range width, power density are big, environmental nonpollution etc.
Advantage, has good application prospect in fields such as Aero-Space, automobile industry, consumer electronics, telecommunication path and electric power.
Compared with material with carbon element double layer capacitor, the pseudocapacitors of sulfide electrode material has higher capacity.Sulfuration
When nickel is as electrode material, electrode surface or body mutually in carry out underpotential deposition, there is chemisorbed or the electricity of high reversible
Chemistry redox reacts the energy storage carried out.Its process is:
Since nickel sulfide is used for energy field, and researcher has synthesized the sulfuration of numerous different-shape by different methods
Nickel material.As disclosed the preparation method of a kind of nanometer nickel sulfide band in Chinese patent application CN102605473A, the method is adopted
Combining with electrostatic spinning technique and sulfurization technology, the nanometer nickel sulfide band of synthesis has good crystallinity.Chinese patent Shen
Please report the chalcogenide of nickel and the preparation method of oxide hollow sphere in CN103058289A, the nickel sulfide of synthesis is hollow
Ball size is about 1 μm.But, the report about the nickel sulfide material of multi-layer hollow structure is little so far, and seldom document report
Road oxide and the transformation technology of sulfide.
Summary of the invention
The present invention provides a kind of hollow sub-microsphere electrode material for super capacitor with multilamellar nickel sulfide shell and system thereof
Preparation Method and application.The hollow nickel sulfide micron ball of multilayer package of synthesis has that specific surface area is big, chemical property is superior
Feature.
The present invention is achieved in that the nickel forerunner preparing solid core shell structure initially with cryogenic fluid sedimentation
Body, under optimum experimental condition, nickel presoma is that the form homoepitaxial with nanometer sheet is in carbon ball surface.It is entered in atmosphere
After row heat treatment, obtain nickel oxide multi-layer hollow structure micron ball, then vulcanize with vulcanizing agent, prepared nickel sulfide multilamellar
Hollow-core construction micron ball.It concretely comprises the following steps:
(1) carbon ball ultrasonic disperse in the mixed solution of water and alcohol organic solvent, soluble nickel salt and carbamide are dissolved in
Wherein, stir certain time in uniform temperature；The precipitated product of generation is centrifuged, cleans and is dried；
(2) step (1) products therefrom, roasting obtains the hollow sub-microsphere of multilamellar nickel oxide shell；
(3) hollow sub-microsphere utilizing the multilamellar nickel oxide shell of step (2) gained mixes with certain proportion with vulcanizing agent,
Calcining under protective atmosphere, products therefrom is the hollow sub-microsphere with multilamellar nickel sulfide shell.
Alcohol organic solvent described in step (1) is the alcohol organic solvent containing hydroxyl: methanol, ethanol or ethylene glycol；Water and
The volume ratio of alcohol organic solvent is 1:1～5:1.
The particle size range of the carbon ball described in step (1) is 500-5000nm.Carbon ball be hydro-thermal method prepare, use glucose or
Sucrose is carbon source, and water is solvent, and in hydrothermal reaction kettle, 140 DEG C of-220 DEG C of temperature ranges heating prepare.
Soluble nickel salt described in step (1) is nickel nitrate, nickel sulfate or Nickel dichloride. etc..
Step (1) described soluble nickel salt, carbon ball is 1:3:12～1:8:32 with the interpolation mol ratio of carbamide.
Step (1) whipping temp is 40～200 DEG C, and mixing time is 1～24 hour.
Step (2) sintering temperature is 300-600 DEG C, and the time is 1～24h, and programming rate is 0.1～10 DEG C/min.
In step (3), the hollow sub-microsphere of multilamellar nickel oxide shell and vulcanizing agent are with nickel/sulfur molar ratio as 1:1～1:5
Mixing.Vulcanizing agent is sulfur powder or thiourea.
Step (3), at 300～600 DEG C, is calcined 1-24 hour in tube furnace.Protective atmosphere is argon.
There is the hollow sub-microsphere of multilamellar nickel sulfide shell, be to be prepared by above-mentioned method.
The application of the described hollow sub-microsphere with multilamellar nickel sulfide shell, is used for preparing electrode of super capacitor.
The method of the synthesis nickel sulfide multi-layer hollow structure micron ball that the present invention provides has the advantage that
Building-up process the most of the present invention uses carbon ball to be template, synthetic product morphology controllable.
2. the present invention uses sulfur powder as vulcanizing agent, and its price is low, and source is wide, and sulfidation is simple.
Synthetic product pattern the most of the present invention is special, is the hollow-core construction micron ball of multilayer package (2-5 layer), micron ball particle diameter
Being distributed homogeneous, specific surface area is big, when being applied to ultracapacitor, has higher specific capacity and stable cycle performance.
Accompanying drawing explanation
The XRD figure of the hollow sub-microsphere of the multilamellar nickel sulfide shell of Fig. 1 embodiment 1；
The scanning electron microscopic picture of the hollow sub-microsphere of the multilamellar nickel sulfide shell of Fig. 2 embodiment 1；
The transmission electron microscope picture of the hollow sub-microsphere of the multilamellar nickel sulfide shell of Fig. 3 embodiment 1；
The cyclic voltammetry curve picture of the hollow sub-microsphere of the multilamellar nickel sulfide shell of Fig. 4 embodiment 1；
The circulation volume picture of the hollow sub-microsphere of the multilamellar nickel sulfide shell of Fig. 5 embodiment 1.
Detailed description of the invention
Embodiment 1
By a diameter of for 50mg 1 μm carbon ball ultrasonic disperse in the mixed solution (volume ratio 1:1) of 100ml water and ethanol, add
Entering 0.2g nickel nitrate and 1g carbamide mix homogeneously, mixed solution stirs 12h under the conditions of 80 DEG C, and products therefrom centrifugation is also used
Deionized water and ethanol purge, then dry 12h in calorstat at 60 DEG C.By gained powder body in atmosphere with the bar of 450 DEG C
Part heat treatment 2h, programming rate is 3 DEG C/min.Gained nickel oxide hollow-core construction micron ball mixes with sulfur powder that (Ni/S mol ratio is
1:1) proceeding in tube furnace, in argon gas atmosphere, condition roasting 4h with 400 DEG C i.e. obtains the hollow micron of multilamellar nickel sulfide shell
Ball.By prepared nickel sulfide material according to 80wt.%, acetylene black 10wt.% and FVDF10wt.% mix homogeneously, make slurry,
It is coated uniformly on nickel screen (1*2cm2On), in 2M potassium hydroxide solution, carry out electrochemical property test after vacuum drying, with sweet
Mercury electrode is reference electrode, and platinum electrode is to electrode.The voltage tester scope of charging and discharging curve and cyclic voltammetry curve be 0～
0.5V.Result shows, it has preferable chemical property.The NiS nano-particle that its result is prepared than hydro-thermal has preferably
Cyclical stability and high rate performance (Nano Energy 2014,5,74 81).
Embodiment 2:
By a diameter of for 50mg 1 μm carbon ball ultrasonic disperse in the mixed solution (volume ratio 2:1) of 100ml water and ethanol, add
Entering 0.3g nickel sulfate and 1g carbamide mix homogeneously, mixed solution stirs 12h under the conditions of 100 DEG C, and products therefrom centrifugation is also
With deionized water and ethanol purge, in calorstat, then at 60 DEG C, dry 12h.By gained powder body in atmosphere with 450 DEG C
Condition heat treatment 2h, programming rate is 3 DEG C/min.Gained nickel oxide hollow-core construction micron ball mixes (Ni/S mol ratio with sulfur powder
For 1:2) proceed in tube furnace, in argon gas atmosphere, the condition roasting 4h with 400 DEG C i.e. obtains the hollow micro-of multilamellar nickel sulfide shell
Rice ball.
Embodiment 3:
By a diameter of for 50mg 1 μm carbon ball ultrasonic disperse in the mixed solution (volume ratio 1:1) of 100ml water and methanol, add
Entering 0.2g nickel nitrate and 1g carbamide mix homogeneously, mixed solution stirs 12h under the conditions of 80 DEG C, and products therefrom centrifugation is also used
Deionized water and ethanol purge, then dry 12h in calorstat at 60 DEG C.By gained powder body in atmosphere with the bar of 500 DEG C
Part heat treatment 2h, programming rate is 3 DEG C/min.Gained nickel oxide hollow-core construction micron ball mixes with thiourea that (Ni/S mol ratio is
1:2) proceeding in tube furnace, in argon gas atmosphere, condition roasting 4h with 400 DEG C i.e. obtains the hollow micron of multilamellar nickel sulfide shell
Ball.
Certainly the present invention also has many embodiments, in the case of spirit and essence, is familiar with this area
Personnel can make corresponding change and deformation, but corresponding change and deformation should belong to the scope of the claims of the present invention.
Claims (10)
1. the preparation method of a hollow sub-microsphere with multilamellar nickel sulfide shell, it is characterised in that comprise the following steps:
(1) carbon ball ultrasonic disperse in the mixed solution of water and alcohol organic solvent, soluble nickel salt and carbamide are dissolved in wherein,
Uniform temperature stirs certain time；The precipitated product of generation is centrifuged, cleans and is dried；
(2) step (1) products therefrom, roasting obtains the hollow sub-microsphere of multilamellar nickel oxide shell；
(3) hollow sub-microsphere utilizing the multilamellar nickel oxide shell of step (2) gained mixes with certain proportion with vulcanizing agent, is protecting
Protecting and calcine under atmosphere, products therefrom is the hollow sub-microsphere with multilamellar nickel sulfide shell.
Preparation method the most according to claim 1, it is characterised in that the alcohol organic solvent described in step (1) is containing hydroxyl
The alcohol organic solvent of base: methanol, ethanol or ethylene glycol；The volume ratio of water and alcohol organic solvent is 1:1～5:1.
Preparation method the most according to claim 1, it is characterised in that the particle size range of the carbon ball described in step (1) is
500-5000nm。
Preparation method the most according to claim 1, it is characterised in that step (1) described soluble nickel salt, carbon ball and carbamide
Interpolation mol ratio be 1:3:12～1:8:32.
Preparation method the most according to claim 1, it is characterised in that step (1) whipping temp is 40～200 DEG C, stirring
Time is 1～24 hour.
Preparation method the most according to claim 1, it is characterised in that step (2) sintering temperature is 300-600 DEG C, the time
Being 1～24h, programming rate is 0.1～10 DEG C/min.
Preparation method the most according to claim 1, it is characterised in that in step (3), multilamellar nickel oxide shell hollow micro-
With nickel/sulfur molar ratio as 1:1～1:5 mixes rice ball with vulcanizing agent.
Preparation method the most according to claim 1, it is characterised in that step (3), at 300～600 DEG C, is calcined in tube furnace
1-24 hour.
9. there is the hollow sub-microsphere of multilamellar nickel sulfide shell, it is characterised in that be by the side described in any one of claim 1-8
Method prepares.
10. the application of the hollow sub-microsphere with multilamellar nickel sulfide shell described in claim 9, it is characterised in that be used for making
Standby electrode of super capacitor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610679098.7A CN106277078B (en) | 2016-08-16 | 2016-08-16 | A kind of hollow sub-microsphere with multilayer nickel sulfide shell and its preparation method and application |
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|---|---|---|---|
| CN201610679098.7A CN106277078B (en) | 2016-08-16 | 2016-08-16 | A kind of hollow sub-microsphere with multilayer nickel sulfide shell and its preparation method and application |
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| CN106277078B CN106277078B (en) | 2018-03-20 |
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Cited By (10)
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|---|---|---|---|---|
| CN107705995A (en) * | 2017-09-29 | 2018-02-16 | 江苏科技大学 | A kind of Mn of height ratio capacity2O3Nano-hollow ball electrode material and preparation method and application |
| CN107833758A (en) * | 2017-10-19 | 2018-03-23 | 山西大学 | A kind of preparation method, product and the application of Ni-based integrated electrode |
| CN108671941A (en) * | 2018-04-17 | 2018-10-19 | 浙江正泰太阳能科技有限公司 | A kind of production hydrogen catalyst and its preparation method and application |
| CN109841423A (en) * | 2019-04-18 | 2019-06-04 | 江西师范大学 | Valence state regulation and surface modification prepare novel barium oxide negative electrode material |
| CN110060873A (en) * | 2019-04-17 | 2019-07-26 | 齐鲁工业大学 | The hollow biological carbon ball base nanometer nickel sulfide rod supercapacitor of one kind and preparation method |
| CN110246700A (en) * | 2019-07-30 | 2019-09-17 | 哈尔滨工业大学 | A kind of preparation method of multi-layer core-shell oxide/sulfide heterojunction structure electrode material |
| CN110391086A (en) * | 2019-07-05 | 2019-10-29 | 太原理工大学 | A method of with solid phase preparing nickelous oxide with microwave mode/nanometer nickel sulfide composite material |
| CN111762821A (en) * | 2020-06-08 | 2020-10-13 | 安徽师范大学 | Hollow micro-nano structure nickel disulfide material, preparation method thereof, aluminum ion battery anode and aluminum ion battery |
| CN112981448A (en) * | 2021-03-03 | 2021-06-18 | 西南大学 | Preparation and application of carbon sphere @ nickel sulfide compound hydrogen evolution catalyst |
| CN114855184A (en) * | 2022-04-29 | 2022-08-05 | 兰州大学 | Water decomposition catalyst and preparation method and application thereof |
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| CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
| CN102605473A (en) * | 2012-02-24 | 2012-07-25 | 长春理工大学 | Preparation method of nickel sulfide nanobelts |
| CN103058289A (en) * | 2013-01-05 | 2013-04-24 | 中南大学 | Method for preparing hollow ball of sulfide and oxide of nickel |
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