CN106710886A - ZnCo2S4 nano material of high-capacity cellular structure, preparation and application thereof - Google Patents
ZnCo2S4 nano material of high-capacity cellular structure, preparation and application thereof Download PDFInfo
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- CN106710886A CN106710886A CN201611186834.1A CN201611186834A CN106710886A CN 106710886 A CN106710886 A CN 106710886A CN 201611186834 A CN201611186834 A CN 201611186834A CN 106710886 A CN106710886 A CN 106710886A
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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 provides a ZnCo2S4 nano material of a high-capacity cellular structure, the preparation and the application thereof, and relates to the field of nano materials. According to the technical scheme of the invention, firstly, a ZnCo2O4 precursor of a cellular structure grows on a foamed nickel substrate through the hydrothermal method. Secondly, the precursor is vulcanized to obtain the ZnCo2S4 nano material of the cellular structure through the hydrothermal method. The ZnCo2S4 nano material of the cellular structure grows directly on the foamed nickel substrate, thus being better in mechanical properties and electrical conductivity. Meanwhile, the ZnCo2S4 nano material is large in specific surface area, and can provide more active sites for the ionic adsorption, the ionic desorption and the redox reaction. The multiple oxidation and reduction reactions of the ZnCo2S4 material are enabled during charging and discharging, so that the material is higher in specific capacitance.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of ZnCo of high power capacity honeycomb2S4Nano material
And its prepare and apply.
Background technology
Ultracapacitor is a kind of energy storage device between ordinary capacitor and chemical cell, has both excellent concurrently
Point, such as power density are high, energy density is high, have extended cycle life, can fast charging and discharging, and with instantaneous high-current discharge and to ring
The characteristic such as border is pollution-free.It is related to the multiple subject such as material, the energy, chemistry, electronic device, the focus as cross discipline research
One of.Used as a kind of environmental protection, the new type of energy storage device of excellent performance, ultracapacitor has in numerous fields widely should
With, the civil area such as including national defence, military project and electric automobile, computer, mobile communication, thus receive countries in the world especially
The great attention of developed country.
From electrode material and the angle of energy stores principle, ultracapacitor can be divided into double electric layers supercapacitor and counterfeit
Electric capacity ultracapacitor.Double layer capacitor is to store electric charge using the interfacial electric double layer formed between electrode and electrolyte,
The number of storing electricity depends on the size of electrode material specific surface area, and double electric layers supercapacitor has big excellent of power density
Point, but its specific capacitance and energy density are smaller, thus limit its range of application.Pseudocapacitors are utilized in electrode material surface
Or the redox reaction of the Rapid reversible of near surface layer generation realizes storing up electricity, the pseudocapacitors compared with double electric layers supercapacitor
Much higher specific capacitance and energy density can be obtained, therefore with good application prospect.Fake capacitance electrode of super capacitor
Material mainly uses transition metal oxide, crosses metal sulfide and conducting polymer.Transient metal sulfide has special
Structure and chemical property, thus held out broad prospects in terms of energy storage.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of ZnCo of honeycomb2S4Nano material, not only has
Good cyclical stability also specific surface area and specific capacitance with superelevation, and prepare simply, it is easy to use.
To realize object above, the present invention is achieved by the following technical programs：
A kind of ZnCo of high power capacity honeycomb2S4Nano material, its pore size be 100~300nm, wall thickness 10~
20nm。
A kind of ZnCo of high power capacity honeycomb2S4The preparation method of nano material, comprises the following steps：
(1) take piece of foam nickel to be cleaned with hydrochloric acid, absolute ethyl alcohol and deionized water successively, then dried at 40~50 DEG C
10~12h, weighs the quality of nickel foam；
(2) Co (NO are weighed respectively3)2, Zn (NO3)2With CO (NH2)2, add in 50mL water, after 15~30min of stirring, obtain
To pale pink solution, nickel foam is put into 60mL reactors, is subsequently poured into pale pink solution, 6 are reacted at 100~160 DEG C
~12h, is cooled to room temperature, cleans drying, obtains pink colour presoma；
(3) by pink colour presoma addition sodium sulfide solution, 4~8h is reacted at 120~140 DEG C, naturally cools to room
Temperature, cleans drying, obtains black product.
Preferably, the length of the nickel foam is 1~4cm, and width is 1~2cm.
Preferably, the Co (NO3)2Concentration be 5~10mM, the Zn (NO3)2Concentration be 2.5~5mM.
Preferably, the cooldown rate of the presoma is 2~5 DEG C/min.
Preferably, the concentration of the vulcanized sodium is 0.01~0.05mol/L.
The present invention also provides a kind of ZnCo of high power capacity honeycomb2S4Nano material is in electrode material for super capacitor
On application.
Beneficial effects of the present invention：The invention provides a kind of ZnCo of honeycomb2S4Nano material has following excellent
Point：(1) it is grown directly upon in foam nickel base, and with the effect from afflux, without using binding agent and conductive agent, this makes it
With more preferably mechanical performance and electric conductivity；(2) specific surface area of honeycomb is big, can be that the adsorption desorption of ion and oxidation are gone back
Original reaction provides more avtive spots；(3) material ZnCo2S4Multiple redox reaction can occur in charge and discharge process.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1：
A kind of ZnCo of high power capacity honeycomb2S4Nano material, its pore size is 300nm, wall thickness 10nm.
The ZnCo of the high power capacity honeycomb2S4The preparation method of nano material, comprises the following steps：
(1) take a piece of 2 × 4cm nickel foams to be cleaned with 6M hydrochloric acid, absolute ethyl alcohol and deionized water successively, then 40~50
10~12h is dried at DEG C, the quality for weighing nickel foam is 187.52mg；
(2) Co (NO are weighed respectively3)2, Zn (NO3)2With CO (NH2)2, add in 50mL water, after 15~30min of stirring, obtain
To pale pink solution, wherein Co (NO3)2Concentration be 10mM, the Zn (NO3)2Concentration be 5mM, nickel foam is put into 60mL
In reactor, pale pink solution is subsequently poured into, 6h is reacted at 140 DEG C, room temperature is cooled to the cooldown rate of 2 DEG C/min, washed
Net drying, obtains pink colour presoma；
(3) by pink colour presoma addition 0.025mol/L sodium sulfide solutions, 6h is reacted at 120 DEG C, is naturally cooled to
Room temperature, cleans drying, obtains weight for 196.72mg black products.
Gained ZnCo2S4Load capacity in nickel foam is 1.15mg/cm-2, the ZnCo of the high power capacity honeycomb2S4
Nano material can be used directly as the electrode of ultracapacitor.
Embodiment 2：
A kind of ZnCo of high power capacity honeycomb2S4Nano material, its pore size is 100nm, wall thickness 10nm.
The ZnCo of the high power capacity honeycomb2S4The preparation method of nano material, comprises the following steps：
(1) take a piece of 1 × 1cm nickel foams to be cleaned with 6M hydrochloric acid, absolute ethyl alcohol and deionized water successively, then 40~50
10~12h is dried at DEG C, the quality for weighing nickel foam is 18.96mg；
(2) Co (NO are weighed respectively3)2, Zn (NO3)2With CO (NH2)2, add in 50mL water, after 15~30min of stirring, obtain
To pale pink solution, wherein Co (NO3)2Concentration be 5mM, the Zn (NO3)2Concentration be 2.5mM, nickel foam is put into
In 60mL reactors, pale pink solution is subsequently poured into, 12h is reacted at 100 DEG C, room is cooled to the cooldown rate of 5 DEG C/min
Temperature, cleans drying, obtains pink colour presoma；
(3) by pink colour presoma addition 0.025mol/L sodium sulfide solutions, 4h is reacted at 140 DEG C, is naturally cooled to
Room temperature, cleans drying, obtains weight for 24.52mg black products.
Gained ZnCo2S4Load capacity in nickel foam is 1.08mg/cm-2, the ZnCo of the high power capacity honeycomb2S4
Nano material can be used directly as the electrode of ultracapacitor.
Embodiment 3：
A kind of ZnCo of high power capacity honeycomb2S4Nano material, its pore size is 250nm, wall thickness 20nm.
The ZnCo of the high power capacity honeycomb2S4The preparation method of nano material, comprises the following steps：
(1) take a piece of 2 × 2cm nickel foams to be cleaned with 6M hydrochloric acid, absolute ethyl alcohol and deionized water successively, then 40~50
10~12h is dried at DEG C, the quality for weighing nickel foam is 98.75mg；
(2) Co (NO are weighed respectively3)2, Zn (NO3)2With CO (NH2)2, add in 50mL water, after 15~30min of stirring, obtain
To pale pink solution, wherein Co (NO3)2Concentration be 4mM, the Zn (NO3)2Concentration be 2mM, nickel foam is put into 60mL
In reactor, pale pink solution is subsequently poured into, 6h is reacted at 160 DEG C, room temperature is cooled to the cooldown rate of 2 DEG C/min, washed
Net drying, obtains pink colour presoma；
(3) by pink colour presoma addition 0.025mol/L sodium sulfide solutions, 8h is reacted at 120 DEG C, is naturally cooled to
Room temperature, cleans drying, obtains weight for 102.95mg black products.
Gained ZnCo2S4Load capacity in nickel foam is 1.05mg/cm-2, the ZnCo of the high power capacity honeycomb2S4
Nano material can be used directly as the electrode of ultracapacitor.
To sum up, the embodiment of the present invention has the advantages that：(1) it is grown directly upon in foam nickel base, and this makes it
With more preferably mechanical performance and electric conductivity；(2) specific surface area of honeycomb is big, can be that the adsorption desorption of ion and oxidation are gone back
Original reaction provides more avtive spots；(3) material ZnCo2S4Multiple redox reaction can occur in charge and discharge process.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposited between operating
In any this actual relation or order.And, term " including ", "comprising" or its any other variant be intended to
Nonexcludability is included, so that process, method, article or equipment including a series of key elements not only will including those
Element, but also other key elements including being not expressly set out, or also include being this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Also there is other identical element in process, method, article or equipment including the key element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic；And these modification or
Replace, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Claims (7)
1. a kind of ZnCo of high power capacity honeycomb2S4Nano material, it is characterised in that its pore size is 100~300nm, wall
10~20nm of thickness.
2. a kind of ZnCo of high power capacity honeycomb as claimed in claim 12S4The preparation method of nano material, its feature exists
In comprising the following steps：
(1) piece of foam nickel is taken to be cleaned with hydrochloric acid, absolute ethyl alcohol and deionized water successively, then dry 10 at 40~50 DEG C~
12h, weighs the quality of nickel foam；
(2) Co (NO are weighed respectively3)2, Zn (NO3)2With CO (NH2)2, add in 50mL water, after 15~30min of stirring, obtain light
Pink colour solution, nickel foam is put into 60mL reactors, is subsequently poured into pale pink solution, at 100~160 DEG C react 6~
12h, is cooled to room temperature, cleans drying, obtains pink colour presoma；
(3) by pink colour presoma addition sodium sulfide solution, 4~8h is reacted at 120~140 DEG C, naturally cools to room temperature, washed
Net drying, obtains black product.
3. the ZnCo of high power capacity honeycomb as claimed in claim 22S4The preparation method of nano material, it is characterised in that institute
The length of nickel foam is stated for 1~4cm, width is 1~2cm.
4. the ZnCo of high power capacity honeycomb as claimed in claim 32S4The preparation method of nano material, it is characterised in that institute
State Co (NO3)2Concentration be 5~10mM, the Zn (NO3)2Concentration be 2.5~5mM.
5. the ZnCo of high power capacity honeycomb as claimed in claim 42S4The preparation method of nano material, it is characterised in that institute
The cooldown rate for stating presoma is 2~5 DEG C/min.
6. the ZnCo of high power capacity honeycomb as claimed in claim 52S4The preparation method of nano material, it is characterised in that,
The concentration of the vulcanized sodium is 0.01~0.05mol/L.
7. the ZnCo of a kind of high power capacity honeycomb as described in claim 2~6 is any2S4Applications to nanostructures, its feature
It is that it can be used directly as the electrode of ultracapacitor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611186834.1A CN106710886A (en) | 2016-12-20 | 2016-12-20 | ZnCo2S4 nano material of high-capacity cellular structure, preparation and application thereof |
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| CN201611186834.1A CN106710886A (en) | 2016-12-20 | 2016-12-20 | ZnCo2S4 nano material of high-capacity cellular structure, preparation and application thereof |
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| CN201611186834.1A Pending CN106710886A (en) | 2016-12-20 | 2016-12-20 | ZnCo2S4 nano material of high-capacity cellular structure, preparation and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601494A (en) * | 2017-02-15 | 2017-04-26 | 安聪聪 | High volume honeycomb nano-material, manufacture of same and super capacitor |
| CN107316757A (en) * | 2017-06-19 | 2017-11-03 | 江苏大学 | A kind of Ni-based NiCo of foam2O4/MoS2Combination electrode material and preparation method thereof |
| CN108609665A (en) * | 2018-05-31 | 2018-10-02 | 安阳师范学院 | Core-shell structure copolymer hollow-core construction zinc-cobalt sulfide nanosphere electrode material and preparation method thereof |
| CN109161925A (en) * | 2018-11-09 | 2019-01-08 | 天津工业大学 | A kind of preparation and Hydrogen Evolution Performance research of 3D structure Zn-Co-S nanocomposite |
| CN110465310A (en) * | 2019-07-03 | 2019-11-19 | 江苏大学 | A kind of cobalt zinc bimetallic sulfide base composite electric catalyst and the preparation method and application thereof |
| CN110943217A (en) * | 2019-12-12 | 2020-03-31 | 安徽师范大学 | Bimetallic sulfide/sulfur particle composite material converted from metal organic framework, preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601494A (en) * | 2017-02-15 | 2017-04-26 | 安聪聪 | High volume honeycomb nano-material, manufacture of same and super capacitor |
| CN107316757A (en) * | 2017-06-19 | 2017-11-03 | 江苏大学 | A kind of Ni-based NiCo of foam2O4/MoS2Combination electrode material and preparation method thereof |
| CN108609665A (en) * | 2018-05-31 | 2018-10-02 | 安阳师范学院 | Core-shell structure copolymer hollow-core construction zinc-cobalt sulfide nanosphere electrode material and preparation method thereof |
| CN109161925A (en) * | 2018-11-09 | 2019-01-08 | 天津工业大学 | A kind of preparation and Hydrogen Evolution Performance research of 3D structure Zn-Co-S nanocomposite |
| CN110465310A (en) * | 2019-07-03 | 2019-11-19 | 江苏大学 | A kind of cobalt zinc bimetallic sulfide base composite electric catalyst and the preparation method and application thereof |
| CN110943217A (en) * | 2019-12-12 | 2020-03-31 | 安徽师范大学 | Bimetallic sulfide/sulfur particle composite material converted from metal organic framework, preparation method and application thereof |
| CN110943217B (en) * | 2019-12-12 | 2022-05-10 | 安徽师范大学 | Bimetallic sulfide/sulfur particle composite material converted from metal organic framework, preparation method and application thereof |
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