CN109036876A - A kind of preparation method of nickel cobalt hydroxide flexible electrode - Google Patents
A kind of preparation method of nickel cobalt hydroxide flexible electrode Download PDFInfo
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- CN109036876A CN109036876A CN201810728020.9A CN201810728020A CN109036876A CN 109036876 A CN109036876 A CN 109036876A CN 201810728020 A CN201810728020 A CN 201810728020A CN 109036876 A CN109036876 A CN 109036876A
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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
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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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- 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
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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
- H01G11/24—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
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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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- 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
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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 present invention relates to a kind of preparation methods of nickel cobalt hydroxide flexible electrode, prepare the mixed solution of nickel salt and cobalt salt first, the carbon nanotube of carbonization/cotton compound is put into and is wherein impregnated, is then mixed into the NH of preparation4Cl and NaOH mixed solution, stand, take out cleaning, drying to get.The present invention uses simple and easy chemical synthesis growth in situ nickel cobalt double-hydroxide on carbon nanotube/cotton composite material of carbonization, so that the flexible electrode of high electrochemical performance is prepared, specific capacitance with higher, and and there is good flexibility.
Description
Technical field
The invention belongs to the preparation field of flexible electrode, in particular to a kind of preparation side of nickel cobalt hydroxide flexible electrode
Method.
Background technique
With the development of society, people propose increasingly higher demands to energy storage, traditional energy storage device is not
It is able to satisfy the demand of people, lighter and thinner more soft energy storage device is current development trend.Therefore, it prepares and to have excellent performance
Flexible electrode becomes the processing key of flexible energy storage device.
Current flexible electrode, which is deposited mainly, two methods of direct the preparation method and indirect the preparation method, and direct the preparation method is first to make
Standby active material is processed into membrane electrode, the advantages of this method is to be lived then by adhesive and film forming matter
Property the high flexible electrode of content of material, but due to the adhesive effect of adhesive, the utilization rate that will lead to active matter is reduced, thus
Lose chemical property；And preparing rule indirectly is the supporting substrates for using flexible material as active material, to prepare flexibility
Electrode, the advantages of this method are the electro-chemical activities that active material is greatly utilized, and adhesive-free adds, but exists again and live
The not strong disadvantage of load capacity of the property material on flexible parent metal low problem and binding strength, thus in order to maximally utilize work
Property material, it is necessary to develop a kind of flexible electrode of new method preparation high load amount.
The active material studied extensively at present mainly has carbon material, conducting polymer and metal oxide three classes, wherein carbon
Material has preferable stability but specific capacitance is lower, and the specific capacitance of conducting polymer is high, but cyclical stability is bad, holds
The expansion and contraction of easy generating material, metal oxide also specific capacitance with higher, and stability height.
Patent CN201610578351.X has invented a kind of nickel cobalt double-hydroxide/NiCo2S4Composite nano materials, by this
Material is used for electrode material for super capacitor, finds its specific capacitance with higher.Patent CN201710049840.0 is proposed
High stable nickel cobalt double-hydroxide electrode material is prepared in microwave synthesizer, but material prepared by both methods is
Powder there are problems that influencing its electro-chemical activity because of the addition of adhesive in electrode production process, thus it is necessary to mention
A kind of method simply preparing electrode out.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation methods of nickel cobalt hydroxide flexible electrode, overcome
Prior art material is powder, while the addition of adhesive influences the defect of electro-chemical activity, this method with the carbon nanotube that is carbonized/
Cotton composite material is flexible parent metal, carries out the preparation of nickel cobalt double-hydroxide, one side carbon material and metallic hydrogen on this basis
The electrode that the combination of oxide obtains has good chemical property, on the other hand the non-powder of the electrode, and there is no because of preparation
Electrode and add the impaired problem of active material chemical property caused by adhesive.
A kind of preparation method of nickel cobalt hydroxide flexible electrode of the invention, step include:
(1) substrate is put into the mixed solution of nickel salt and cobalt salt, is impregnated；Wherein substrate is carbon nanotube/cotton of carbonization
Compound；
(2) under room temperature, NH is prepared4Then the mixed solution of Cl and NaOH is added in step (1), in 50-65 DEG C of item
It stands, cleans under part, dry to get nickel cobalt hydroxide flexible electrode.
The preferred embodiment of above-mentioned preparation method is as follows:
Carbon nanotube/cotton the compound being carbonized in the step (1):
The preparation of carbon nano-tube solution: carboxylic carbon nano-tube and neopelex are added with the ratio of 1:1
Into deionized water, stirring, ultrasonic 1h is finally dispersed using homogenizer, obtains carbon nano tube dispersion liquid.
The preparation of carbon nanotube/cotton compound: cotton fabric is placed on prepared carbon nano-tube solution with the bath raio of 1:2
It is handled in infrared proof machine, treatment conditions are that 5 DEG C/min is warming up to 135 DEG C, handle 70min；It then takes out, 100
It is dried in DEG C baking oven；It finally washes, room temperature is dried.
Carbonization carbon nanotube/cotton compound preparation: carbon nanotube/cotton compound is placed on to different high polymer aqueous solutions
In, 5min is impregnated, tube furnace is sent into after drying and carries out carbonization treatment, treatment conditions are as follows: 5 DEG C/min heating, 900 DEG C of heat preservation 1h.
After cooling, setup test is taken out.
Step (1) nickel salt is NiCl2；Cobalt salt is CoCl2。
The concentration of nickel salt is 10~20g/L in mixed solution in the step (1)；The concentration of cobalt salt is 3~4g/L.
Soaking time is 20-35min in the step (1).
NH in mixed solution in the step (2)4The concentration of Cl is 20-25g/L, NaOH concentration 4-5g/L.
The nickel salt, cobalt salt, NH4The molar ratio relationship of Cl, NaOH are 0.5-2:15-40:2-6:0.5-2.
It is preferred that the nickel source, cobalt source, NH4The molar ratio relationship of Cl, NaOH are about 1:30:4:1.
Time of repose is 30min-24h in the step (2), and the preferably time is for 24 hours.
A kind of nickel cobalt hydroxide flexible electrode of the method preparation of the invention.
The nickel cobalt hydroxide be honeycomb structure, independent nanometer sheet with a thickness of 38-47nm, diameter 500-
630nm。
A kind of application of nickel cobalt hydroxide flexible electrode of the invention.
For inventor by many tests, discovery this method can not be by NiCl2、CoCl2、NH4Cl and NaOH directly mixes system
It is standby, it is surprising that the difference of the sequence and method that are added will will lead to the Different Results of experiment, or even failure.
Beneficial effect
(1) present invention is using the carbon nanotube after being carbonized/cotton composite material as flexible parent metal, and uses on this basis mild
Simple method carries out the preparation of nickel cobalt double-hydroxide, obtains the flexible electrode of high electrochemical activity, capacitance is higher；
(2) present invention has good electric conductivity, has played on the basis of the carbon nanotube of carbonization/cotton compound
The afflux of effect acts on, while its good adsorptivity, and can lay a good foundation for the growth of nickel cobalt hydroxide, and two
The combination of person, so that the carbon nanotube/cotton compound and honeycomb nickel cobalt hydroxide of carbonization have all played bigger effect, and
Synergistic effect is generated, nickel cobalt is using the carbon nanotube/cotton compound being carbonized as substrate, and upper herein to grow nickel cobalt compound, the two exists
In electro-chemical test, nickel cobalt hydroxide mainly provides energy storage, generates electronics, and the high conductivity of carbon material can accelerate electronics
Transmitting, play bigger energy storage effect, specific capacitance may be up to 811F g-1In the prior art, nickel cobalt hydroxide is mostly powder,
Different with flexible electrode prepared by this patent, the capacitance of previous material is higher, but form is powder, and this patent
Being researched and developed is flexible electrode, such as in the prior art (Flexible Zn2SnO4/MnO2core/shell nanocable-
carbon microfiber hybrid composites for high-performance supercapacitor
Electrodes) capacitance of electrode obtained in a text is 621.6F g-1(2mV s-1), two kinds of gold are used in the material
Belong to oxide, but capacitance is high still without this patent, therefore the patent provides new approaches for the preparation of flexible electrode；
(3) present invention, using its good adsorptivity, inhales first on the basis of the carbon nanotube of carbonization/cotton compound
Attached nickel chromium triangle ion, is then added alkaline solution, on the compositions growth in situ nickel cobalt hydroxide, and this method is simple and easy, has
Not in traditional hydrothermal synthesis method, have the advantages that low energy consumption, and easy industrialization large-scale production, great application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of flexible electrode prepared by the present invention；Wherein (a) embodiment 1, (b) embodiment 2 are (c) real
Example 3 is applied, (d) embodiment 4；
Fig. 2 is cyclic voltammetry curve of the embodiment 4 under different scanning rates；
Fig. 3 is charging and discharging curve of the embodiment 4 under different current densities；
Fig. 4 is the bending state picture of embodiment 4；Wherein a, b respectively indicate (a, tiled state, b, bending state).
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The NiCl of 0.24g is prepared first2With the CoCl of 0.078g2Mixed solution, by the carbon nanotube of carbonization/cotton compound
It is put into and wherein impregnates 30min, then prepare the NH of 0.428g4The NaOH mixed solution of Cl and 0.101g, is mixed into NiCl2With
CoCl2Mixed solution in, stand the regular hour under the conditions of 55 DEG C, cleaned after taking-up with deionized water, dry, complete.
Then in the KOH solution of 2M, using prepared electrode as working electrode, platinized platinum is to electrode, and calomel electrode is
Reference electrode carries out electrochemical property test.
Wherein, the time that Examples 1 to 4 reaction is stood is respectively 30min, 3h, 12h and for 24 hours, other reaction conditions are same
On.
By scanning electron microscope (SEM) photograph (Fig. 1) as can be seen that the reaction time be nickel cobalt hydroxide honeycomb structure for 24 hours the most
Completely, therefore example 4 is best anti-for the size (diameter 500-630nm) of independent nanometer sheet and thickness (with a thickness of 38-47nm)
Between seasonable, relevant electro-chemical test is then carried out to it, Fig. 2 is cyclic voltammetry curve test chart, can be clear from figure
The redox peaks for seeing material, the exactly performance of nickel cobalt hydroxide chemical property, Fig. 3 is charge-discharge test, can be with
See, with the increase of current density, the charge and discharge time is gradually reduced, this is because in general, smaller current density
It can make electrode material that there is better responsiveness (analyzing Fig. 1,2).By calculating, the single electrode electricity of the electrode material
Holding is 811F g-1(0.1Ag-1), 611.83 (0.3A g-1), 436.06 (0.5Ag-1), 338.16 (0.7Ag-1), 269.72
(0.9Ag-1) material the advantages of be embodied in flexible and two aspect of high specific capacitance.
Claims (10)
1. a kind of preparation method of nickel cobalt hydroxide flexible electrode, step include:
(1) substrate is put into the mixed solution of nickel salt and cobalt salt, is impregnated；Wherein substrate is that carbon nanotube/cotton of carbonization is compound
Object；
(2) under normal temperature condition, NH is prepared4Then the mixed solution of Cl and NaOH is added in step (1), under the conditions of 50-65 DEG C
It stands, cleaning is dried to get nickel cobalt hydroxide flexible electrode.
2. preparation method according to claim 1, which is characterized in that step (1) nickel salt is NiCl2；Cobalt salt is
CoCl2。
3. preparation method according to claim 1, which is characterized in that in the step (1) in mixed solution nickel salt it is dense
Degree is 10~20g/L；The concentration of cobalt salt is 3~4g/L.
4. preparation method according to claim 1, which is characterized in that soaking time is 20-35min in the step (1).
5. preparation method according to claim 1, which is characterized in that NH in mixed solution in the step (2)4Cl's is dense
Degree is 20-25g/L, NaOH concentration 4-5g/L.
6. preparation method according to claim 1, which is characterized in that the nickel salt, cobalt salt, NH4The molar ratio of Cl, NaOH
Example relationship is 0.5-2:15-40:2-6:0.5-2.
7. preparation method according to claim 1, which is characterized in that time of repose is 30min- in the step (2)
24h。
8. a kind of nickel cobalt hydroxide flexible electrode of claim 1 the method preparation.
9. flexible electrode according to claim 8, which is characterized in that the nickel cobalt hydroxide is honeycomb structure, single
Only nanometer sheet with a thickness of 38-47nm, diameter 500-630nm.
10. a kind of application of nickel cobalt hydroxide flexible electrode.
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| CN201810728020.9A CN109036876A (en) | 2018-07-05 | 2018-07-05 | A kind of preparation method of nickel cobalt hydroxide flexible electrode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111899988A (en) * | 2020-08-06 | 2020-11-06 | 合肥工业大学 | Macro preparation method and application of nickel-cobalt double-metal hydroxide electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106847530A (en) * | 2017-02-27 | 2017-06-13 | 四川大学 | A kind of nickel cobalt base-carbon nano tube combination electrode material and preparation method thereof |
| CN107068416A (en) * | 2016-12-08 | 2017-08-18 | 北京印刷学院 | A kind of preparation method of carbon material/metal hydroxides combination electrode material |
-
2018
- 2018-07-05 CN CN201810728020.9A patent/CN109036876A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068416A (en) * | 2016-12-08 | 2017-08-18 | 北京印刷学院 | A kind of preparation method of carbon material/metal hydroxides combination electrode material |
| CN106847530A (en) * | 2017-02-27 | 2017-06-13 | 四川大学 | A kind of nickel cobalt base-carbon nano tube combination electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TIANQI HAO,ET AL.: ""Hierarchical NiCo layered double hydroxides nanosheets on carbonized CNT/cotton as a high-performance flexible supercapacitor"", 《J MATER SCI》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111899988A (en) * | 2020-08-06 | 2020-11-06 | 合肥工业大学 | Macro preparation method and application of nickel-cobalt double-metal hydroxide electrode material |
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