CN107195483A - A kind of preparation method of the NiO/ Nano carbon balls with core shell structure - Google Patents

A kind of preparation method of the NiO/ Nano carbon balls with core shell structure Download PDF

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CN107195483A
CN107195483A CN201710320025.3A CN201710320025A CN107195483A CN 107195483 A CN107195483 A CN 107195483A CN 201710320025 A CN201710320025 A CN 201710320025A CN 107195483 A CN107195483 A CN 107195483A
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nio
shell structure
core shell
sio
nano carbon
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CN107195483B (en
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甘礼华
甘源
刘明贤
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Tongji University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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 present invention relates to a kind of preparation method of the NiO/ Nano carbon balls with core shell structure.By 0.3~1.2：100：31.6：0.05~0.25：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, Nickelous nitrate hexahydrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, by ammoniacal liquor, water and absolute ethyl alcohol add Nickelous nitrate hexahydrate after mixing, stir 10~120min, sequentially add resorcinol and cetyl trimethylammonium bromide, stir and formalin and tetraethyl orthosilicate are added after 30min, stir 24h after at 100 DEG C hydro-thermal reaction 24h, then it is placed in tube furnace, under nitrogen atmosphere, 1~10 DEG C/min heating rate is from room temperature to 700~900 DEG C of carbonizations, the NaOH solution for being finally 3mol/L with concentration removes the SiO in product2, obtain the NiO/ Nano carbon balls with core shell structure；Present invention process is simple, easy to operate, during as electrode material for super capacitor, shows higher specific capacitance and preferable cyclical stability.

Description

A kind of preparation method of the NiO/ Nano carbon balls with core shell structure
Technical field
The present invention relates to a kind of preparation method of the NiO/ Nano carbon balls with core shell structure, belong to material preparation technology neck Domain.
Background technology
Energy problem receives significant attention in recent years, and ultracapacitor is because its is environment-friendly, the spy that has extended cycle life etc. Point, there is good application prospect in terms of energy automobile and consumer electronics product.Porous carbon materials are because of its specific surface area The advantages of height, good conductivity, Stability Analysis of Structures, is as the electrode material for super capacitor for applying more, but porous carbon materials are deposited In the not high shortcoming of specific capacitance.Comparatively, transition metal oxide such as nickel oxide, manganese oxide etc., with cheap, raw material The advantages of wide material sources, high specific capacitance, but there is also the deficiencies such as cyclical stability difference simultaneously.Therefore, transiting metal oxidation is studied Thing/carbon composite, the two advantage is combined, and is a focus of current electrode material for super capacitor research.For example, " one Plant the preparation method of oxidation nickel carbon bead composite " (Chinese invention patent, application number：201510190340.X) with orderly Mesoporous carbon bead is carrier, and reflow treatment is carried out first in NaOH solution, then obtains hydrogen using Hydrolysis Reactions of Metal-ions synthesis Nickel carbon bead is aoxidized, heat treatment is finally combined, oxidation nickel carbon bead composite has been made.A kind of " electrode of super capacitor The preparation method of the mesoporous Nano carbon balls of material Ni O/ " (Chinese invention patent, application number：201610055611.5) it is first by SiO2 Colloidal sol after nickel salt stirring, hydro-thermal with obtaining NiO/SiO2Nano-particle, then again to obtained NiO/SiO2Added in nano-particle Resorcinol and formalin, are again stirring for, obtain containing NiO/SiO after hydro-thermal process2Polymer nanocomposite ball, last carbon Change, remove SiO2The mesoporous Nano carbon balls of NiO/ are obtained after template.However, to there is preparation method more multiple for these microballoon composites Miscellaneous the shortcomings of, as the former needs reflow treatment, the latter needs two step hydro-thermals, and these all improve technology difficulty and complex operation journey Degree.
The content of the invention
It is an object of the invention to disclose a kind of preparation method of the NiO/ Nano carbon balls with core shell structure.Use this method The NiO/ Nano carbon balls electrode materials with core shell structure prepared, simple with preparation technology, specific capacitance is high, cyclical stability Can be good the advantages of.
To reach above-mentioned purpose, Nickelous nitrate hexahydrate is first distributed to three solution bodies of ammoniacal liquor, absolute ethyl alcohol, water by the present invention Nickel ammonia chelate is formed in system, in the hydrolysis of follow-up tetraethyl orthosilicate, polymerization and resorcinol and oxymethylene polymerization process In, nickel ammonia chelate is by SiO2Nano-particle parcel is distributed in core-shell polymer nanosphere, through carbonization, removes SiO2After obtain NiO/ Nano carbon balls.The specific capacitance of composite can be greatly improved in the fake capacitance that NiO is brought, with mesoporous, microcellular structure carbon Shell, can effectively prevent NiO seepages, and improve the stable circulation performance of electrode material.
Concrete technology is carried out as follows：
By 0.3~1.2：100：31.6：0.05~0.25：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, anhydrous Ethanol, Nickelous nitrate hexahydrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammonia Water, water and absolute ethyl alcohol are well mixed, add Nickelous nitrate hexahydrate and stir 10~120min, sequentially add resorcinol and 16 Alkyl trimethyl ammonium bromide, continues to stir 30min, then adds after formalin and tetraethyl orthosilicate, stirring 24h 100 Hydro-thermal reaction 24h at DEG C, obtains containing NiO and SiO2The polymer nanocomposite ball of nano-particle；It is placed in tube furnace, in nitrogen Under atmosphere, 1~10 DEG C/min heating rate, from room temperature to 700~900 DEG C of carbonizations, is finally 3mol/L's with concentration NaOH solution removes the SiO in product2, obtain the NiO/ Nano carbon balls with core shell structure；
Above raw material is commercially available technical grade product.
The consumption of wherein NaOH solution is the SiO in product212 times of quality.
Analysis test result shows that gained has the NiO/ Nano carbon balls of core shell structure uniform in size, good dispersion, diameter About 600nm, specific surface area 750m2/ more than g.
The invention has the advantages that：
1. Nickelous nitrate hexahydrate is first dispersed in formation nickel ammonia in three solution systems of ammoniacal liquor, absolute ethyl alcohol and water by this method Chelate, nickel ammonia chelate is by SiO in the hydrolysis of tetraethyl orthosilicate and polymerization process2Nano-particle is wrapped up, and can prevent NiO Assemble and reduced by carbon material during high temperature cabonization, and can effectively prevent the reunion of NiO nano-particles, NiO quilts can be made The NiO/ Nano carbon balls with core shell structure uniformly coated.
What 2. the present invention was obtained contains NiO and SiO2The polymer nanocomposite ball of nano-particle, through carbonization, removes SiO2After obtain The specific capacitance of composite can be greatly improved in NiO/ Nano carbon balls, the fake capacitance that NiO is brought, with mesoporous, microcellular structure carbon Shell, can effectively prevent NiO seepages, and improve the stable circulation performance of electrode material.
3. the present invention is prepared by one-step method only to be needed once in the NiO/ Nano carbon balls with core shell structure, preparation process Hydro-thermal and once it is carbonized, has the advantages that technique is simple, operating process is easy.
4. the NiO/ Nano carbon balls with core shell structure prepared by the present invention are uniform in size, good dispersion, diameter is about 600nm, specific surface area 750m2/ more than g.When NiO/ Nano carbon balls with core shell structure are as electrode material for super capacitor, Analysis and tests show that, under 1.0A/g during discharge and recharge, its specific capacitance reaches the appearance after more than 350F/g, cycle charge-discharge 5000 times Conservation rate is measured more than 90%, higher specific capacitance and preferable cyclical stability is shown.
Embodiment
Embodiment 1
By 0.3：100：31.6：0.05：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydrations Nickel nitrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous Ethanol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 10min, is sequentially added resorcinol and cetyl trimethyl bromination Ammonium, continues to stir 30min, then adds after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction at 100 DEG C 24h, obtains containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 1 DEG C/ Min heating rate is finally removed in product from room temperature to 700 DEG C of carbonizations with the NaOH solution that concentration is 3mol/L SiO2, obtain the NiO/ Nano carbon balls with core shell structure.The consumption of above-mentioned NaOH solution is the SiO in product2The 12 of quality Times.
Embodiment 2
By 0.6：100：31.6：0.1：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydration nitre Sour nickel, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous second Alcohol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 30min, is sequentially added resorcinol and cetyl trimethylammonium bromide, Continue to stir 30min, then add after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction 24h at 100 DEG C, obtain To containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 4 DEG C/min liter Warm speed is from room temperature to 750 DEG C of charings, and the NaOH solution for being finally 3mol/L with concentration removes the SiO in product2, obtain NiO/ Nano carbon balls with core shell structure；The consumption of above-mentioned NaOH solution is the SiO in product212 times of quality.
Embodiment 3
By 0.9：100：31.6：0.2：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydration nitre Sour nickel, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous second Alcohol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 80min, is sequentially added resorcinol and cetyl trimethylammonium bromide, Continue to stir 30min, then add after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction 24h at 100 DEG C, obtain To containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 8 DEG C/min liter Warm speed is from room temperature to 800 DEG C of carbonizations, and the NaOH solution for being finally 3mol/L with concentration removes the SiO in product2, obtain NiO/ Nano carbon balls with core shell structure.The consumption of above-mentioned NaOH solution is the SiO in product212 times of quality.
Embodiment 4
By 1.2：100：31.6：0.25：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydrations Nickel nitrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous Ethanol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 120min, is sequentially added resorcinol and cetyl trimethyl bromination Ammonium, continues to stir 30min, then adds after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction at 100 DEG C 24h, obtains containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 10 DEG C/ Min heating rate is finally removed in product from room temperature to 900 DEG C of carbonizations with the NaOH solution that concentration is 3mol/L SiO2, obtain the NiO/ Nano carbon balls with core shell structure.The consumption of NaOH solution is the SiO in product212 times of quality.
Analysis test result shows that the NiO/ Nano carbon balls with core shell structure that embodiment 1-4 is obtained are uniform in size, point Dissipate property good, diameter about 600nm, specific surface area 750m2/ more than g.The NiO/ carbon with core shell structure that embodiment 1-4 is obtained Nanosphere presses 8 with graphite and polytetrafluoroethylene (PTFE)：1：1 mass ratio is measured, and is dissolved in after ground and mixed is uniform in ethanol solution, ultrasound Vibrate 1h formation slurries.The slurry is uniformly coated in nickel foam, and obtained in 80 DEG C of oven drying 24h with nucleocapsid The NiO/ Nano carbon balls electrode material for super capacitor of structure.Using the NiO/ Nano carbon balls with core shell structure as working electrode, Nickel foam is that, to electrode, Hg/HgO electrodes are reference electrode.KOH with electrochemical workstation (CHI 660D) in 6mol/L is electrolysed In liquid, in 25 DEG C of specific capacitance values in potential window -1.0~NiO/ Nano carbon balls electrode material of the 0V tests with core shell structure With cycle charge discharge electrical property.Test result shows that gained has the NiO/ Nano carbon balls of core shell structure as super capacitor electrode Pole material, under 1.0A/g during discharge and recharge, the capability retention that specific capacitance reaches after more than 350F/g, cycle charge-discharge 5000 times exists More than 90%, show higher specific capacitance and preferable cyclical stability.
Above raw material is commercially available technical grade product.
Above-mentioned hydro-thermal reaction refers to：Reactant is fitted into the stainless steel water heating kettle of inner liner polytetrafluoroethylene and carried out at hydro-thermal Reason reaction.

Claims (1)

1. a kind of preparation method of the NiO/ Nano carbon balls with core shell structure, it is characterised in that：Ammonia is measured by quality parts ratio Water：Water：Absolute ethyl alcohol：Nickelous nitrate hexahydrate：Tetraethyl orthosilicate：Formalin：Resorcinol：Cetyl trimethyl bromination Ammonium=0.3~1.2：100：31.6：0.05~0.25：4.7：1.4：1：1, then, ammoniacal liquor, water and absolute ethyl alcohol are first mixed equal It is even, Nickelous nitrate hexahydrate is added, 10~120min is stirred, sequentially adds resorcinol and cetyl trimethylammonium bromide, Continue to stir 30min, then add formalin and tetraethyl orthosilicate, be stirred for after 24h the hydro-thermal reaction 24h at 100 DEG C, Obtain containing NiO and SiO2The polymer nanocomposite ball of nano-particle, is placed in tube furnace, under nitrogen atmosphere, with 1~10 DEG C/min heating rate from room temperature to 700~900 DEG C of carbonizations, the NaOH solution for being finally 3mol/L with concentration removes production SiO in thing2, obtain the NiO/ Nano carbon balls with core shell structure；
Above-mentioned hydro-thermal reaction refers to：Reactant is fitted into progress hydro-thermal process in the stainless steel water heating kettle of inner liner polytetrafluoroethylene anti- Should；
The consumption of above-mentioned NaOH solution is the SiO in product212 times of quality；
Above-mentioned raw materials are commercially available technical grade product.
CN201710320025.3A 2017-05-09 2017-05-09 A kind of preparation method of the NiO/ Nano carbon balls with nucleocapsid Expired - Fee Related CN107195483B (en)

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Cited By (6)

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CN108232167A (en) * 2018-01-19 2018-06-29 洛阳理工学院 A kind of carbon@ferrosilites hollow-core construction compound and preparation method thereof
CN109985643A (en) * 2019-03-19 2019-07-09 贵州大学 A kind of add in-place bromine preparation small size PdKBrThe method of@HSC
CN110828190A (en) * 2018-08-10 2020-02-21 南京理工大学 Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof
CN111377431A (en) * 2020-03-19 2020-07-07 上海交通大学 Morphology-controllable-adjustable nitrogen-loaded carbon nanocapsule and preparation method and application thereof
CN113096966A (en) * 2021-04-16 2021-07-09 广德天运新技术股份有限公司 High-specific-capacity supercapacitor electrode material based on silicon dioxide and preparation method thereof
CN114583140A (en) * 2022-05-05 2022-06-03 潍坊科技学院 Nickel disulfide/silicon composite material with core-shell structure and preparation method and application thereof

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CN105217601A (en) * 2015-11-05 2016-01-06 北京工业大学 A kind of preparation method with the porous hollow carbon ball of high-specific surface area
CN105702484A (en) * 2016-01-27 2016-06-22 同济大学 A manufacturing method for a NiO/mesoporous carbon nanosphere which is supercapacitor electrode materials
CN105752966A (en) * 2016-01-27 2016-07-13 同济大学 Preparation method of graphene/hollow carbon nanometer balls
CN105819422A (en) * 2016-03-17 2016-08-03 南京理工大学 Preparation method of nitrogen doped hollow mesoporous carbon sphere

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CN103427073A (en) * 2013-08-05 2013-12-04 同济大学 Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material
CN105217601A (en) * 2015-11-05 2016-01-06 北京工业大学 A kind of preparation method with the porous hollow carbon ball of high-specific surface area
CN105702484A (en) * 2016-01-27 2016-06-22 同济大学 A manufacturing method for a NiO/mesoporous carbon nanosphere which is supercapacitor electrode materials
CN105752966A (en) * 2016-01-27 2016-07-13 同济大学 Preparation method of graphene/hollow carbon nanometer balls
CN105819422A (en) * 2016-03-17 2016-08-03 南京理工大学 Preparation method of nitrogen doped hollow mesoporous carbon sphere

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108232167A (en) * 2018-01-19 2018-06-29 洛阳理工学院 A kind of carbon@ferrosilites hollow-core construction compound and preparation method thereof
CN108232167B (en) * 2018-01-19 2020-06-09 洛阳理工学院 Carbon @ iron silicate hollow structure compound and preparation method thereof
CN110828190A (en) * 2018-08-10 2020-02-21 南京理工大学 Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof
CN110828190B (en) * 2018-08-10 2022-02-18 南京理工大学 Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof
CN109985643A (en) * 2019-03-19 2019-07-09 贵州大学 A kind of add in-place bromine preparation small size PdKBrThe method of@HSC
CN111377431A (en) * 2020-03-19 2020-07-07 上海交通大学 Morphology-controllable-adjustable nitrogen-loaded carbon nanocapsule and preparation method and application thereof
CN113096966A (en) * 2021-04-16 2021-07-09 广德天运新技术股份有限公司 High-specific-capacity supercapacitor electrode material based on silicon dioxide and preparation method thereof
CN114583140A (en) * 2022-05-05 2022-06-03 潍坊科技学院 Nickel disulfide/silicon composite material with core-shell structure and preparation method and application thereof
CN114583140B (en) * 2022-05-05 2022-06-28 潍坊科技学院 Nickel disulfide/silicon composite material with core-shell structure and preparation method and application thereof

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