CN106277078B - A kind of hollow sub-microsphere with multilayer nickel sulfide shell and its preparation method and application - Google Patents
A kind of hollow sub-microsphere with multilayer nickel sulfide shell and its preparation method and application Download PDFInfo
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- CN106277078B CN106277078B CN201610679098.7A CN201610679098A CN106277078B CN 106277078 B CN106277078 B CN 106277078B CN 201610679098 A CN201610679098 A CN 201610679098A CN 106277078 B CN106277078 B CN 106277078B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of hollow sub-microsphere with multilayer nickel sulfide shell and its preparation method and application, nickel presoma is grown on carbon ball surface using the cryogenic fluid precipitation method first, calcining obtains the hollow sub-microsphere of multilayer nickel oxide shell in atmosphere, vulcanizes nickel oxide micron ball in tube furnace obtain the hollow sub-microsphere of complete multilayer nickel sulfide shell afterwards.The hollow-core construction of unique multilayer package not only contributes to effective infiltration of electrolyte, while electrolyte and active material can be made fully to contact, so as to improve the chemical property of material.The hollow nickel sulfide micron ball of multilayer package prepared by the present invention, which is used as electrode material for super capacitor, 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 multilayer nickel sulfide shell and preparation method thereof and in super capacitor
Application in device.
Background technology
Ultracapacitor also known as electrochemical capacitor, it 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 is wide, power density is big, environmental nonpollution etc.
Advantage, there is good application prospect in fields such as Aero-Space, automobile industry, consumer electronics, telecommunication path and electric power.
Compared with carbon material double layer capacitor, the pseudocapacitors of sulfide electrode material have higher capacity.Vulcanization
When nickel is as electrode material, underpotential deposition is carried out in electrode surface or body phase, the chemisorbed or electricity of high reversible occurs
The energy storage that chemistry redox reaction is carried out.Its process is:
Since nickel sulfide is used for energy field, researcher has synthesized the vulcanization of numerous different-shapes by different methods
Nickel material.As disclosed a kind of preparation method of nanometer nickel sulfide band in Chinese patent application CN102605473A, this method is adopted
It is combined with electrostatic spinning technique and sulfurization technology, the nanometer nickel sulfide band of synthesis has good crystallinity.Chinese patent Shen
The chalcogenide of nickel and the preparation method of oxide hollow sphere please be reported in CN103058289A, the nickel sulfide of synthesis is hollow
Ball size is about 1 μm.However, the report of the vulcanization nickel material about multi-layer hollow structure is seldom so far, and seldom document report
The transformation technology of road oxide and sulfide.
The content of the invention
The present invention provides a kind of hollow sub-microsphere electrode material for super capacitor and its system with multilayer nickel sulfide shell
Preparation Method and application.The hollow nickel sulfide micron ball of the 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 for preparing solid core shell structure using cryogenic fluid sedimentation first
Body, under optimum experimental condition, nickel presoma be in the form of nanometer sheet homoepitaxial in carbon ball surface.It is entered in atmosphere
After row heat treatment, nickel oxide multi-layer hollow structure micron ball is obtained, then is vulcanized with vulcanizing agent, has prepared nickel sulfide multilayer
Hollow-core construction micron ball.It is concretely comprised the following steps：
(1) soluble nickel salt and urea are dissolved in by carbon ball ultrasonic disperse in the mixed solution of water and alcohol organic solvent
Wherein, certain time is stirred in certain temperature；By the precipitated product centrifugation of generation, cleaning and dry；
(2) step (1) products therefrom, roasting obtain the hollow sub-microsphere of multilayer nickel oxide shell；
(3) mixed using the hollow sub-microsphere of the multilayer nickel oxide shell obtained by step (2) with vulcanizing agent with certain proportion,
Calcined under protective atmosphere, products therefrom is the hollow sub-microsphere with multilayer 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 carbon ball described in step (1) is 500-5000nm.Carbon ball is made for hydro-thermal method, using glucose or
Sucrose is carbon source, and water is solvent, and 140 DEG C of -220 DEG C of temperature ranges heating are obtained in hydrothermal reaction kettle.
Soluble nickel salt described in step (1) is nickel nitrate, nickel sulfate or nickel chloride etc..
The addition mol ratio of step (1) described soluble nickel salt, carbon ball and urea is 1:3:12~1:8:32.
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 and vulcanizing agent of multilayer nickel oxide shell are using nickel/sulphur molar ratio as 1:1~1:5
Mixing.Vulcanizing agent is sulphur powder or thiocarbamide.
Step (3) calcines 1-24 hours at 300~600 DEG C in tube furnace.Protective atmosphere is argon gas.
Hollow sub-microsphere with multilayer nickel sulfide shell, it is prepared by above-mentioned method.
The application of the described hollow sub-microsphere with multilayer nickel sulfide shell, for preparing electrode of super capacitor.
The method of synthesis nickel sulfide multi-layer hollow structure micron ball provided by the invention has advantages below：
1. building-up process of the present invention uses carbon ball as template, synthetic product morphology controllable.
2. the present invention is using sulphur powder as vulcanizing agent, its price is low, and source is wide, and sulfidation is simple.
It is the hollow-core construction micron ball of multilayer package (2-5 layers) 3. synthetic product pattern of the present invention is special, micron ball particle diameter
It is distributed homogeneous, specific surface area is big, during applied to ultracapacitor, has higher specific capacity and stable cycle performance.
Brief description of the drawings
The XRD of the hollow sub-microsphere of the multilayer nickel sulfide shell of Fig. 1 embodiments 1；
The scanning electron microscopic picture of the hollow sub-microsphere of the multilayer nickel sulfide shell of Fig. 2 embodiments 1；
The transmission electron microscope picture of the hollow sub-microsphere of the multilayer nickel sulfide shell of Fig. 3 embodiments 1；
The cyclic voltammetry curve picture of the hollow sub-microsphere of the multilayer nickel sulfide shell of Fig. 4 embodiments 1；
The circulation volume picture of the hollow sub-microsphere of the multilayer nickel sulfide shell of Fig. 5 embodiments 1.
Embodiment
Embodiment 1
By a diameter of 1 μm of carbon ball ultrasonic disperse of 50mg in the mixed solution of 100ml water and ethanol (volume ratio 1:1) in, add
Enter 0.2g nickel nitrates and 1g urea is well mixed, mixed solution stirs 12h under the conditions of 80 DEG C, and products therefrom, which centrifuges, to be used in combination
Deionized water and ethanol cleaning, then dry 12h in insulating box at 60 DEG C.By gained powder in atmosphere with 450 DEG C of bar
Part is heat-treated 2h, and programming rate is 3 DEG C/min.Gained nickel oxide hollow-core construction micron ball mixes that (Ni/S mol ratios are with sulphur powder
1:1) it is transferred in tube furnace, the hollow micron of multilayer nickel sulfide shell is produced with 400 DEG C of condition roasting 4h in argon gas atmosphere
Ball.Obtained vulcanization nickel material is well mixed according to 80wt.%, acetylene black 10wt.% and FVDF10wt.%, slurry is made,
It is coated uniformly on nickel screen (1*2cm2) on, electrochemical property test is carried out after vacuum drying in 2M potassium hydroxide solutions, 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.As a result show, it has preferable chemical property.Its result has more preferable than NiS nano particles prepared by hydro-thermal
Cyclical stability and high rate performance (Nano Energy 2014,5,74-81).
Embodiment 2：
By a diameter of 1 μm of carbon ball ultrasonic disperse of 50mg in the mixed solution of 100ml water and ethanol (volume ratio 2:1) in, add
Enter 0.3g nickel sulfates and 1g urea is well mixed, mixed solution stirs 12h under the conditions of 100 DEG C, and products therefrom centrifuges simultaneously
Cleaned with deionized water and ethanol, then dry 12h at 60 DEG C in insulating box.By gained powder in atmosphere with 450 DEG C
Condition is heat-treated 2h, and programming rate is 3 DEG C/min.Gained nickel oxide hollow-core construction micron ball mixes (Ni/S mol ratios with sulphur powder
For 1:2) it is transferred in tube furnace, the hollow micro- of multilayer nickel sulfide shell is produced with 400 DEG C of condition roasting 4h in argon gas atmosphere
Rice ball.
Embodiment 3：
By a diameter of 1 μm of carbon ball ultrasonic disperse of 50mg in the mixed solution of 100ml water and methanol (volume ratio 1:1) in, add
Enter 0.2g nickel nitrates and 1g urea is well mixed, mixed solution stirs 12h under the conditions of 80 DEG C, and products therefrom, which centrifuges, to be used in combination
Deionized water and ethanol cleaning, then dry 12h in insulating box at 60 DEG C.By gained powder in atmosphere with 500 DEG C of bar
Part is heat-treated 2h, and programming rate is 3 DEG C/min.Gained nickel oxide hollow-core construction micron ball mixes that (Ni/S mol ratios are with thiocarbamide
1:2) it is transferred in tube furnace, the hollow micron of multilayer nickel sulfide shell is produced with 400 DEG C of condition roasting 4h in argon gas atmosphere
Ball.
Certainly the present invention also has many embodiments, in the case of without prejudice to spirit and essence, is familiar with this area
Personnel can make corresponding change and deformation, but corresponding change and deformation should belong to scope of the claims of the invention.
Claims (8)
1. a kind of preparation method of the hollow sub-microsphere with multilayer nickel sulfide shell, it is characterised in that comprise the following steps：
(1) soluble nickel salt and urea are dissolved in wherein by carbon ball ultrasonic disperse in the mixed solution of water and alcohol organic solvent,
Certain time is stirred at 80-100 DEG C；By the precipitated product centrifugation of generation, cleaning and dry；
(2) step (1) products therefrom, roasting obtain the hollow sub-microsphere of multilayer nickel oxide shell；
(3) mixed, protected with certain proportion with vulcanizing agent using the hollow sub-microsphere of the multilayer nickel oxide shell obtained by step (2)
Calcined under shield atmosphere, products therefrom is the hollow sub-microsphere with multilayer nickel sulfide shell；
Alcohol organic solvent described in step (1) is the alcohol organic solvent containing hydroxyl：Methanol, ethanol or ethylene glycol；Water and alcohol have
The volume ratio of solvent is 1：1~5:1；
The addition mol ratio of step (1) described soluble nickel salt, carbon ball and urea is 1:3:12~1:8:32；
2. preparation method according to claim 1, it is characterised in that the particle size range of the carbon ball described in step (1) is
500-5000nm。
3. preparation method according to claim 1, it is characterised in that step (1) mixing time is 1~24 hour.
4. preparation method according to claim 1, it is characterised in that step (2) sintering temperature is 300-600 DEG C, the time
For 1~24h, programming rate is 0.1~10 DEG C/min.
5. preparation method according to claim 1, it is characterised in that in step (3), multilayer nickel oxide shell it is hollow micro-
Rice ball is with vulcanizing agent using nickel/sulphur molar ratio as 1：1~1：5 mixing.
6. preparation method according to claim 1, it is characterised in that step (3) is calcined at 300~600 DEG C in tube furnace
1-24 hours.
7. the hollow sub-microsphere with multilayer nickel sulfide shell, it is characterised in that be as the side described in claim any one of 1-6
What method was prepared.
8. the application of the hollow sub-microsphere with multilayer nickel sulfide shell described in claim 7, it is characterised in that for preparing
Electrode of super capacitor.
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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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| 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 |
| CN107833758B (en) * | 2017-10-19 | 2019-07-23 | 山西大学 | A kind of preparation method and application of Ni-based integrated electrode |
| CN108671941B (en) * | 2018-04-17 | 2021-10-01 | 浙江正泰太阳能科技有限公司 | Hydrogen production catalyst and preparation method and application thereof |
| CN110060873B (en) * | 2019-04-17 | 2020-12-08 | 齐鲁工业大学 | Hollow biochar sphere-based nickel sulfide nanorod supercapacitor and preparation method thereof |
| CN109841423B (en) * | 2019-04-18 | 2022-03-04 | 江西师范大学 | Preparation of novel vanadium oxide negative electrode material by valence state regulation and surface modification |
| CN110391086B (en) * | 2019-07-05 | 2020-12-18 | 太原理工大学 | Method for preparing nickel oxide/nickel sulfide nano composite material by solid phase microwave 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 |
| CN111762821B (en) * | 2020-06-08 | 2023-04-25 | 安徽师范大学 | Hollow micro-nano structure nickel disulfide material and 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 |
| CN114855184B (en) * | 2022-04-29 | 2023-07-18 | 兰州大学 | Water splitting catalyst and its prepn and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2016-08-16 CN CN201610679098.7A patent/CN106277078B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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