CN105355463B - A kind of preparation method of flexible super capacitor electrode and device - Google Patents
A kind of preparation method of flexible super capacitor electrode and device Download PDFInfo
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- CN105355463B CN105355463B CN201510755898.8A CN201510755898A CN105355463B CN 105355463 B CN105355463 B CN 105355463B CN 201510755898 A CN201510755898 A CN 201510755898A CN 105355463 B CN105355463 B CN 105355463B
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- nickel foam
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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 preparation method of a kind of flexible super capacitor electrode and device, belongs to function element preparing technical field.Including：First, it uses alkaline buffer, diluted acid, organic solvent, acid solution, absolute ethyl alcohol, deionized water to clean perforated metal piece successively, dries；Perforated metal piece after cleaning pressurizes 3 6min under 2 5MPa pressure, and pressed perforated metal piece is soaked in corresponding reaction dissolvent for use；The perforated metal piece being soaked in reaction dissolvent is taken, it is dry in perforated metal on piece growth activity material, obtain flexible super capacitor electrode of the present invention.The present invention uses the sequence opposite with conventional method, compression process first is carried out to the perforated metal piece after cleaning, then growth activity material on it again, pressed perforated metal piece porosity reduces, the growth of active material only carries out on perforated metal piece surface, so that the flexibility of perforated metal piece has obtained good holding, can be widely used in flexible electronic devices.
Description
Technical field
The invention belongs to function element preparing technical fields, and in particular to a kind of super electricity based on perforated metal piece substrate
The preparation method of container electrode and device.
Background technology
Ultracapacitor (supercapacitor) is between battery and traditional capacitor, energy fast charging and discharging, base
In the energy-storage travelling wave tube of Cathode/Solution Interface electrochemical process.Due to high energy density, longer service life cycle,
The advantages that environmental-friendly and safe, ultracapacitor are widely used to traffic, mobile communication, information technology, aviation boat
The fields such as it.With the generation of Novel electronic devices that are more and more wearable or can winding, such as Electronic Paper, foldable display
Device and other multimedia devices etc., it is also more and more urgent for the demand of flexible energy storage device, thus flexible super capacitor
Research is increasingly paid attention to by researcher.Compared with conventional Super capacitor, flexible super capacitor not only needs electrode material
Material has good chemical property, it is often more important that need electrode material applied to flexible super capacitor in bending or
The performance kept under the states such as folding.
In order to realize the buckle resistance energy of flexible super capacitor, need to choose with good flexibility, electric conductivity and
There is the flexible substrate of preferable binding force with active material.Perforated metal piece is by physically or chemically method in porous substrate material table
One layer of metal is covered in face and inside, a kind of perforated metal material obtained from porous substrate material is then removed, with good
Electric conductivity and flexibility, have been widely used in the preparation of flexible super capacitor.Currently, preparing based on perforated metal piece
It is first in the perforated metal on piece growth activity substance cleaned up, then tabletting obtains super electricity when electrode of super capacitor
Container electrode.However, due in perforated metal piece there are larger hole, reaction dissolvent during growth activity substance easily into
Enter and react with metal material inside hole, the flexibility of perforated metal substrate is influenced, to limit poroid sheet metal soft
The extensive use in property energy storage device field.
Invention content
In view of the defects in the background art, the present invention proposes a kind of ultracapacitors based on perforated metal piece substrate
The preparation method of electrode and device.Compacting of the present invention by changing poroid sheet metal in electrode production process sequentially, is being grown
Poroid sheet metal is suppressed before active material, reduces aperture and the porosity of perforated metal piece, it is molten to avoid reaction
Agent is reacted with internal metallic material, the electrochemistry for the ultracapacitor for making its flexibility obtain good holding, and obtaining
Performance also has larger promotion.
Technical scheme is as follows：
A kind of preparation method of flexible super capacitor electrode, includes the following steps：
The cleaning of step 1, perforated metal piece：Alkaline buffer removal perforated metal piece surface oxide layer, dilute is used successively
Acid neutralizes alkaline buffer and removing oxide layer, organic solvent removal surface grease, acid solution is further gone thoroughly to remove removing oxide layer simultaneously
And enhancing surface reaction activity, absolute ethyl alcohol and deionized water remove surface cleaning agent, then dry；
The compacting of step 2, perforated metal piece：Perforated metal piece after being cleaned to step 1 carries out compression process, pressure size
For 2-5MPa, pressing time 3-6min；Pressed perforated metal piece is soaked in corresponding reaction dissolvent for use；
The growth of step 3, active material：The perforated metal piece being soaked in reaction dissolvent is taken, is given birth in perforated metal on piece
Long acting material, it is dry, obtain flexible super capacitor electrode of the present invention.
Further, perforated metal piece described in step 1 is foam metal, strainer metal etc., and the foam metal is foam
Nickel, Foam silver etc..
Further, alkaline buffer described in step 1 is NaOH-Na2CO3、Na2CO3-NaHCO3Deng；The diluted acid is dilute
Hydrochloric acid, dilute sulfuric acid etc.；The organic solvent is ethylene glycol, glycerine etc., and the acid solution is hydrochloric acid, sulfuric acid etc..
Further, removing oxide layer is thoroughly removed described in step 1 and enhance a concentration of dilute of the acid solution of surface reaction activity
2 times of acid concentration.
Further, the solvent used when the corresponding reaction dissolvent of step 2 is step 3 growth activity material, specifically
For ethylene glycol, ethylenediamine etc..
Further, hydro-thermal method, solvent-thermal method, electricity can be used in perforated metal on piece growth activity material described in step 3
The methods of plating method；The active material is carbon-based material, conducting polymer, transistion metal compound, conducting polymer and carbon materials
The composite material of material, the composite material of conducting polymer and transition metal oxide, carbon material and transition metal oxide are answered
Condensation material etc., specially graphene, MnO2, PANI etc..
Further, the active material that perforated metal on piece described in step 3 is grown is homogenous material or two or more materials
Material；When preparing the active material being made of two or more materials, the general method using substep growth obtains.
A kind of preparation method of flexible super capacitor, includes the following steps：
The cleaning of step 1, perforated metal piece：Alkaline buffer removal perforated metal piece surface oxide layer, dilute is used successively
Acid neutralizes alkaline buffer and removing oxide layer, organic solvent removal surface grease, acid solution is further gone thoroughly to remove removing oxide layer simultaneously
And enhancing surface reaction activity, absolute ethyl alcohol and deionized water remove surface cleaning agent, then dry；
The compacting of step 2, perforated metal piece：Perforated metal piece after being cleaned to step 1 carries out compression process, pressure size
For 2-5MPa, pressing time 3-6min；Pressed perforated metal piece is soaked in corresponding reaction dissolvent for use；
The growth of step 3, active material：The perforated metal piece being soaked in reaction dissolvent is taken, is given birth in perforated metal on piece
Long acting material, it is dry, obtain flexible super capacitor electrode of the present invention；
Step 4：The perforated metal piece for the active material of growth that step 3 is obtained as upper/lower electrode, according on to
Under sequence the perforated metal piece of the perforated metal piece for growing active material, diaphragm and the active material of growth is stacked in one
It rises, is then injected into electrolyte, air locking is to get to flexible super capacitor of the present invention.
Further, perforated metal piece described in step 1 is foam metal, strainer metal etc., and the foam metal is foam
Nickel, Foam silver etc..
Further, alkaline buffer described in step 1 is NaOH-Na2CO3、Na2CO3-NaHCO3Deng；The diluted acid is dilute
Hydrochloric acid, dilute sulfuric acid etc.；The organic solvent is ethylene glycol, glycerine etc., and the acid solution is hydrochloric acid, sulfuric acid etc..
Further, removing oxide layer is thoroughly removed described in step 1 and enhance a concentration of dilute of the acid solution of surface reaction activity
2 times of acid concentration.
Further, the solvent used when the corresponding reaction dissolvent of step 2 is step 3 growth activity material, specifically
For ethylene glycol, ethylenediamine etc..
Further, hydro-thermal method, solvent-thermal method, electricity can be used in perforated metal on piece growth activity material described in step 3
The methods of plating method；The active material is carbon-based material, conducting polymer, transistion metal compound, conducting polymer and carbon materials
The composite material of material, the composite material of conducting polymer and transition metal oxide, carbon material and transition metal oxide are answered
Condensation material etc., specially graphene, MnO2, PANI etc..
Further, the active material that perforated metal on piece described in step 3 is grown is homogenous material or two or more materials
Material；When preparing the active material being made of two or more materials, the general method using substep growth obtains.
Further, electrolyte described in step 4 is ultracapacitor common electrolyte, such as gel electrolyte, liquid electrolytic
Matter or ionic liquid etc., specially KOH, Na2SO4、H2SO4、PVA–H3PO4Deng.
Beneficial effects of the present invention are：
1, the present invention uses the sequence opposite with conventional method, i.e., first carries out compression process to poroid sheet metal, then again
Growth activity material on it, pressed perforated metal piece porosity reduce, and the growth of active material is only in perforated metal piece
Surface carries out so that the flexibility of perforated metal piece has obtained good holding, can be widely used in flexible electronic devices.And it passes
System method in unstamped perforated metal piece surface growth activity substance, due to perforated metal piece have larger porosity and
Aperture, reaction dissolvent, which can enter inside poroid sheet metal, to react, and destroys the structure inside perforated metal piece, obtained band
The perforated metal piece flexibility of active material substantially reduces.
2, the present invention has carried out thorough cleaning to poroid sheet metal before growth activity material and has been stored in subsequent anti-
It answers in solvent, this aspect avoids the oxidation of perforated metal piece, improves and is grown on the equal of perforated metal on piece active material
Even property and binding force；On the other hand, the process dried using vacuum drying chamber before use is also avoided, step is simplified, is dropped
Low cost.
Description of the drawings
Fig. 1 is the knot of the ultracapacitor assembled after the poroid sheet metal growth activity material of flexibility provided by the invention
Structure schematic diagram, wherein 1 perforated metal piece (hole of a representatives with active material with active material obtained for the method for the present invention
Shape metal part, b represent the perforated metal part of not long acting material), 3 be the diaphragm for being soaked with electrolyte；
Fig. 2 is the structural representation of the ultracapacitor assembled after conventional flex perforated metal piece growth activity material
Figure, wherein the 2 perforated metal pieces with active material obtained for conventional method, 3 be the diaphragm for being soaked with electrolyte；
Fig. 3 is the cyclic voltammetry curve comparison diagram for the flexible super capacitor electrode that embodiment 1 and comparative example 1 obtain；
Fig. 4 is the cyclic voltammetry curve comparison diagram for the flexible super capacitor electrode that embodiment 2 and comparative example 2 obtain.
Specific implementation mode
With reference to the accompanying drawings and examples, technical scheme of the present invention is described in detail.
Embodiment 1
For the poroid sheet metal of flexibility used in the present embodiment for nickel foam, which is commercially available nickel foam, is had good
Good electric conductivity, flexibility and reactivity.
A kind of preparation method of flexible super capacitor electrode, includes the following steps：
The cleaning of step 1, nickel foam：The nickel foam (0.1600g) for taking 2cm × 2cm, uses mass fraction for 5% successively
NaOH and 5%Na2CO3Alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethyl alcohol, deionized water to nickel foam carry out ultrasound
Cleaning, the ultrasonic time of each cleaning agent is 10min, is dried；
The compacting of step 2, nickel foam：Nickel foam after being cleaned to step 1 using tablet press machine carries out compression process, and pressure is
2MPa, pressing time 4min；Pressed nickel foam is soaked in ethylene glycol for use；
The growth of step 3, active material：The nickel foam being soaked in ethylene glycol is taken, carries out the life of active material on it
It is long；Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stirs evenly, then adds 8mL anhydrous ethylenediamines,
30min is stirred, mixed liquor is obtained；Mixed liquor is transferred in ptfe autoclave, step 2 is placed into and is stored in ethylene glycol
Nickel foam in solution, then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；After taking out reaction
The nickel foam for growing active material is placed in drying box 70 DEG C after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%
Dry 6h is to get to the nickel foam with NiSe active materials.
A kind of preparation method of flexible super capacitor, includes the following steps：
The cleaning of step 1, nickel foam：The nickel foam (0.1600g) for taking 2cm × 2cm, uses mass fraction for 5% successively
NaOH and 5%Na2CO3Alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethyl alcohol, deionized water to nickel foam carry out ultrasound
Cleaning, the ultrasonic time of each cleaning agent is 10min, is dried；
The compacting of step 2, nickel foam：Nickel foam after being cleaned to step 1 using tablet press machine carries out compression process, and pressure is
2MPa, pressing time 4min；Pressed nickel foam is soaked in ethylene glycol for use；
The growth of step 3, active material：The nickel foam being soaked in ethylene glycol is taken, carries out the life of active material on it
It is long；Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stirs evenly, then adds 8mL anhydrous ethylenediamines,
30min is stirred, mixed liquor is obtained；Mixed liquor is transferred in ptfe autoclave, step 2 is placed into and is stored in ethylene glycol
Nickel foam in solution, then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；After taking out reaction
The nickel foam for growing active material is placed in drying box 70 DEG C after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%
Dry 6h is to get to the nickel foam with NiSe active materials；
Step 4：The nickel foam for the band NiSe active materials that step 3 is obtained is as upper/lower electrode, according to from top to bottom
Sequence stacks the nickel foam with NiSe active materials, filter paper diaphragm and nickel foam with NiSe active materials, then notes
Enter electrolyte, air locking is to get to flexible super capacitor of the present invention.
Comparative example 1
It uses conventional method to prepare flexible super capacitor by substrate of nickel foam, specifically includes following steps：
The cleaning of step 1, nickel foam：The nickel foam (0.1600g) of 2cm × 2cm is taken, dilute hydrochloric acid is used successively, acetone, goes
Ionized water is cleaned by ultrasonic nickel foam, and the ultrasonic time of each cleaning agent is 10min, is then done in vacuum drying chamber
It is dry；
The growth of step 2, active material：The growth activity substance in step 1 cleaning and dry nickel foam；Detailed process
For：0.0800g selenium powders are added in 8mL ethylene glycol, stir evenly, then add 8mL anhydrous ethylenediamines, stirs 30min, obtains
To mixed liquor；Mixed liquor is transferred in ptfe autoclave, places into step 1 cleaning and dry nickel foam, then
At 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；Take out the foam that active material is grown after reacting
Nickel is placed in drying box 70 DEG C of dry 6h to get to based on bubble using deionized water and 95% ethyl alcohol alternately after cleaning 5 times
The flexible super capacitor electrode of foam nickel substrate；
Step 3, the nickel foam progress compression process for growing active material to step 2 using tablet press machine, pressure 2MPa,
Pressing time is 4min；
Step 4：It is suitable according to from top to bottom using the pressed nickel foam with active material of step 3 as upper/lower electrode
Sequence stacks the nickel foam with active material, filter paper diaphragm and nickel foam with active material, is then injected into electrolyte, close
Device is sealed, the flexible super capacitor is obtained.
Fig. 3 is the cyclic voltammetry curve comparison diagram for the flexible super capacitor electrode that embodiment 1 and comparative example 1 obtain；Point
The electrode of super capacitor that the electrode of super capacitor and comparative example 1 not obtained using embodiment 1 obtain is as working electrode, in 6M
Cyclic voltammetry is carried out using two-probe method in KOH solution, wherein scanning voltage is 0~0.8V, sweep speed 5mV/s.
Since under same scan speed, the graphics area that cyclic voltammetry curve surrounds is bigger, capacitive property is better；From the figure 3, it may be seen that
Under same scan speed, the area of the cyclic voltammetry curve of 1 electrode of embodiment is bigger than the area of 1 cyclic voltammetry curve of comparative example,
Show that the flexible super capacitor that embodiment 1 obtains has better performance.
Embodiment 2
For the poroid sheet metal of flexibility used in the present embodiment for nickel foam, which is commercially available nickel foam, is had good
Good electric conductivity, flexibility and reactivity.
To prepare NiSe, NiCo in foam nickel base2S4For the electrode of super capacitor of active material, including with
Lower step：
The cleaning of step 1, nickel foam：The nickel foam (0.1600g) for taking 2cm × 2cm, uses mass fraction for 5% successively
NaOH and 5%Na2CO3Alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethyl alcohol, deionized water to nickel foam carry out ultrasound
Cleaning, the ultrasonic time of each cleaning agent is 10min, is dried；
The compacting of step 2, nickel foam：Nickel foam after being cleaned to step 1 using tablet press machine carries out compression process, and pressure is
2MPa, pressing time 4min；Pressed nickel foam is soaked in ethylene glycol for use；
The growth of step 3, NiSe active materials：The nickel foam being soaked in ethylene glycol is taken, carries out active material on it
Growth；Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stir evenly, then add the anhydrous second of 8mL two
Amine stirs 30min, obtains mixed liquor；Mixed liquor is transferred in ptfe autoclave, step 2 is placed into and is stored in second
Nickel foam in glycol solution, then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；It takes out anti-
The nickel foam that active material should be grown afterwards is placed in after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95% in drying box
70 DEG C of dry 6h are to get to the nickel foam with NiSe active materials；
Step 4, NiCo2S4The growth of active material：It is grown in the nickel foam for the band NiSe active materials that step 3 obtains
NiCo2S4Active material, detailed process are：By 54.525mg Ni (NO3)2·6H2O、109.136mg Co(NO3)2·6H2O、
157.714mg HMT (four hexamine of ring pregnancy) are added in 75mL deionized waters, stir 30min, obtain mixed liquor；Mixed liquor is turned
It moves in ptfe autoclave, places into the nickel foam for the band NiSe active materials that step 3 obtains, then the water at 95 DEG C
Thermal response 8h, after the completion of reaction, cooled to room temperature obtains nickel cobalt forerunner in the nickel foam with NiSe active materials
Body takes out, and after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%, is placed in 60 DEG C of dry 5h in drying box；It will
45.034mg Na2S·9H2O is dissolved in 75mL deionized waters, is stirred 30min, is obtained Na2S solution；By Na2S solution shifts
Into ptfe autoclave, the nickel foam obtained above with nickel cobalt presoma and NiSe active materials is placed into, then
The hydro-thermal reaction 8h at 120 DEG C, after the completion of reaction, cooled to room temperature, i.e., in the nickel foam with NiSe active materials
To NiCo2S4Active material takes out, and after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%, is placed in drying box 60 DEG C
Dry 5h has NiSe and NiCo to get to growth2S4The nickel foam of two kinds of active materials.
Band NiSe, NiCo2S4The nickel foam of active material is the preparation method of the flexible super capacitor of electrode, including with
Lower step：
The cleaning of step 1, nickel foam：The nickel foam (0.1600g) for taking 2cm × 2cm, uses mass fraction for 5% successively
NaOH and 5%Na2CO3Alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethyl alcohol, deionized water to nickel foam carry out ultrasound
Cleaning, the ultrasonic time of each cleaning agent is 10min, is dried；
The compacting of step 2, nickel foam：Nickel foam after being cleaned to step 1 using tablet press machine carries out compression process, and pressure is
2MPa, pressing time 4min；Pressed nickel foam is soaked in ethylene glycol for use；
The growth of step 3, NiSe active materials：The nickel foam being soaked in ethylene glycol is taken, carries out active material on it
Growth；Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stir evenly, then add the anhydrous second of 8mL two
Amine stirs 30min, obtains mixed liquor；Mixed liquor is transferred in ptfe autoclave, step 2 is placed into and is stored in second
Nickel foam in glycol solution, then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；It takes out anti-
The nickel foam that active material should be grown afterwards is placed in after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95% in drying box
70 DEG C of dry 6h are to get to the nickel foam with NiSe active materials；
Step 4, NiCo2S4The growth of active material：It is grown in the nickel foam for the band NiSe active materials that step 3 obtains
NiCo2S4Active material, detailed process are：By 54.525mg Ni (NO3)2·6H2O、109.136mg Co(NO3)2·6H2O、
157.714mg HMT (four hexamine of ring pregnancy) are added in 75mL deionized waters, stir 30min, obtain mixed liquor；Mixed liquor is turned
It moves in ptfe autoclave, places into the nickel foam for the band NiSe active materials that step 3 obtains, then the water at 95 DEG C
Thermal response 8h, after the completion of reaction, cooled to room temperature obtains nickel cobalt forerunner in the nickel foam with NiSe active materials
Body takes out, and after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%, is placed in 60 DEG C of dry 5h in drying box；It will
45.034mg Na2S·9H2O is dissolved in 75mL deionized waters, is stirred 30min, is obtained Na2S solution；By Na2S solution shifts
Into ptfe autoclave, the nickel foam obtained above with nickel cobalt presoma and NiSe active materials is placed into, then
The hydro-thermal reaction 8h at 120 DEG C, after the completion of reaction, cooled to room temperature, i.e., in the nickel foam with NiSe active materials
To NiCo2S4Active material takes out, and after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%, is placed in drying box 60 DEG C
Dry 5h has NiSe and NiCo to get to growth2S4The nickel foam of two kinds of active materials；
Step 5：The growth that step 4 obtains there are into NiSe and NiCo2S4The nickel foam of two kinds of active materials is as power-on and power-off
Growth is had NiSe and NiCo by pole in accordance with the order from top to bottom2S4Nickel foam, filter paper diaphragm and the growth of two kinds of active materials
There are NiSe and NiCo2S4The nickel foam of two kinds of active materials stacks, and is then injected into electrolyte, and air locking is to get to this hair
The bright flexible super capacitor.
Comparative example 2
Conventional method is used to prepare with band NiSe, NiCo2S4The nickel foam of active material is the flexible super capacitance of electrode
Device specifically includes following steps：
The cleaning of step 1, nickel foam：The nickel foam (0.1600g) of 2cm × 2cm is taken, dilute hydrochloric acid is used successively, acetone, goes
Ionized water is cleaned by ultrasonic nickel foam, and the ultrasonic time of each cleaning agent is 10min, is then done in vacuum drying chamber
It is dry；
The growth of step 2, NiSe active materials：NiSe active materials are cleaned and are grown in dry nickel foam in step 1,
Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stirs evenly, then adds 8mL anhydrous ethylenediamines, stir
30min obtains mixed liquor；Mixed liquor is transferred in ptfe autoclave, step 1 cleaning and dry foam are placed into
Nickel, then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；Active material is grown after taking out reaction
The nickel foam of material, using deionized water and 95% ethyl alcohol alternately after cleaning 5 times, be placed in drying box 70 DEG C of dry 6h to get
To the nickel foam with NiSe active materials；
Step 3, NiCo2S4The growth of active material：It is grown in the nickel foam for the band NiSe active materials that step 2 obtains
NiCo2S4Active material, detailed process are：By 54.5250mg Ni (NO3)2·6H2O、109.1360mg Co(NO3)2·6H2O、
157.714mg HMT (four hexamine of ring pregnancy) are added in 75mL deionized waters, stir 30min, obtain mixed liquor；Mixed liquor is turned
It moves in ptfe autoclave, places into the nickel foam for the band NiSe active materials that step 2 obtains, then the water at 95 DEG C
Thermal response 8h, after the completion of reaction, cooled to room temperature obtains nickel cobalt forerunner in the nickel foam with NiSe active materials
Body takes out, and after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%, is placed in 60 DEG C of dry 5h in drying box；It will
45.0340mg Na2S·9H2O is dissolved in 75mL deionized waters, is stirred 30min, is obtained Na2S solution；By Na2S solution shifts
Into ptfe autoclave, the nickel foam obtained above with nickel cobalt presoma and NiSe active materials is placed into, then
The hydro-thermal reaction 8h at 120 DEG C, after the completion of reaction, cooled to room temperature, i.e., in the nickel foam with NiSe active materials
To NiCo2S4Active material takes out, and after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%, is placed in drying box 60 DEG C
Dry 5h has NiSe and NiCo to get to growth2S4The nickel foam of two kinds of active materials；
Step 4 has NiSe and NiCo using tablet press machine to the growth that step 3 obtains2S4The nickel foam of two kinds of active materials into
Row compression process, pressure 2MPa, pressing time 4min；
Step 5, by the pressed band NiSe and NiCo of step 42S4The nickel foam of two kinds of active materials as upper/lower electrode,
In accordance with the order from top to bottom by pressed band NiSe and NiCo2S4Nickel foam, filter paper diaphragm and the compacting of two kinds of active materials
Band NiSe and NiCo afterwards2S4The nickel foam of two kinds of active materials stacks, and is then injected into electrolyte, and air locking obtains institute
State flexible super capacitor.
Fig. 4 is the cyclic voltammetry curve comparison diagram for the flexible super capacitor electrode that embodiment 2 and comparative example 2 obtain；Point
The electrode of super capacitor that the electrode of super capacitor and comparative example 2 not obtained using embodiment 2 obtain is as working electrode, in 6M
Cyclic voltammetry is carried out using two-probe method in KOH solution, wherein scanning voltage is 0~0.8V, sweep speed 5mV/s.
Since under same scan speed, the graphics area that cyclic voltammetry curve surrounds is bigger, capacitive property is better；As shown in Figure 4, exist
Under same scan speed, the area of the cyclic voltammetry curve of 2 electrode of embodiment is bigger than the area of 2 cyclic voltammetry curve of comparative example,
Show that the flexible super capacitor that embodiment 2 obtains has better performance.
Fig. 1 and Fig. 2 is respectively the structural schematic diagram for the flexible super capacitor that the present invention and conventional method obtain；By Fig. 1
It is interior with Fig. 2 it is found that the flexible super capacitor electrode that the present invention obtains, only grows active material on perforated metal piece surface
The flexibility of portion's perforated metal piece has obtained good holding, helps to improve its flexibility；And the flexibility that conventional method obtains is super
Grade electrode for capacitors, since there is perforated metal piece larger porosity and aperture, reaction dissolvent can enter in poroid sheet metal
Portion makes perforated metal piece surface and inside grow active material, destroys the structure inside perforated metal piece, obtained band
The perforated metal piece flexibility of active material substantially reduces.
The present invention uses the sequence opposite with conventional method, i.e., first carries out compression process to poroid sheet metal, then exist again
Growth activity material thereon, pressed perforated metal piece porosity reduce, and the growth of active material is only in perforated metal piece table
Face carries out so that the flexibility of perforated metal piece has obtained good holding, can be widely used in flexible electronic devices；In life
Thorough cleaning has been carried out to poroid sheet metal before long acting material and has been stored in subsequent reaction dissolvent, has been completely cut off using solvent
The mode of air preserves perforated metal piece, avoids the oxidation of perforated metal piece, improves and is grown on perforated metal on piece activity
The uniformity and binding force of substance；The method of the present invention is easy to operate, at low cost, easily realizes industrialization large-scale production.
Claims (5)
1. a kind of preparation method of flexible super capacitor electrode, includes the following steps：
The cleaning of step 1, nickel foam：It is defoamed in nickel surface oxide layer, diluted acid using alkaline buffer successively and alkalinity is slow
Fliud flushing and further go that removing oxide layer, organic solvent removal surface grease, acid solution thoroughly remove removing oxide layer and to enhance surface anti-
Activity, absolute ethyl alcohol and deionized water removal surface cleaning agent are answered, is then dried；
The compacting of step 2, nickel foam：Nickel foam after being cleaned to step 1 carries out compression process, and pressure size 2-5MPa adds
The pressure time is 3-6min；Pressed nickel foam is soaked in ethylene glycol for use；
The growth of step 3, active material：The nickel foam being soaked in ethylene glycol is taken, grows work in nickel foam using hydro-thermal method
Property material；Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stir evenly, then add the anhydrous second of 8mL two
Amine stirs 30min, obtains mixed liquor；Mixed liquor is transferred in ptfe autoclave, the nickel foam of step is placed into,
Then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；Active material is grown after taking out reaction
Nickel foam is placed in 70 DEG C of dry 6h in drying box, obtains band after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%
The nickel foam of NiSe active materials, the as described electrode of super capacitor.
2. the preparation method of flexible super capacitor electrode according to claim 1, which is characterized in that alkali described in step 1
Property buffer solution be NaOH-Na2CO3、Na2CO3-NaHCO3；The diluted acid is dilute hydrochloric acid, dilute sulfuric acid；The organic solvent is second two
Alcohol, glycerine, the acid solution are hydrochloric acid, sulfuric acid.
3. the preparation method of flexible super capacitor electrode according to claim 1, which is characterized in that sour described in step 1
2 times of a concentration of dilute acid concentration of liquid.
4. the preparation method of flexible super capacitor electrode according to claim 1, which is characterized in that living described in step 3
Property material be carbon-based material, conducting polymer, transistion metal compound, conducting polymer and carbon material composite material, conduction
The composite material of the composite material of polymer and transition metal oxide, carbon material and transition metal oxide.
5. a kind of preparation method of flexible super capacitor, includes the following steps：
The cleaning of step 1, nickel foam：It is defoamed in nickel surface oxide layer, diluted acid using alkaline buffer successively and alkalinity is slow
Fliud flushing and further go that removing oxide layer, organic solvent removal surface grease, acid solution thoroughly remove removing oxide layer and to enhance surface anti-
Activity, absolute ethyl alcohol and deionized water removal surface cleaning agent are answered, is then dried；
The compacting of step 2, nickel foam：Nickel foam after being cleaned to step 1 carries out compression process, and pressure size 2-5MPa adds
The pressure time is 3-6min；Pressed nickel foam is soaked in ethylene glycol for use；
The growth of step 3, active material：The nickel foam being soaked in ethylene glycol is taken, grows work in nickel foam using hydro-thermal method
Property material；Detailed process is：0.0800g selenium powders are added in 8mL ethylene glycol, stir evenly, then add the anhydrous second of 8mL two
Amine stirs 30min, obtains mixed liquor；Mixed liquor is transferred in ptfe autoclave, the nickel foam of step is placed into,
Then at 140 DEG C hydro-thermal reaction for 24 hours, after the completion of reaction, cooled to room temperature；Active material is grown after taking out reaction
Nickel foam is placed in 70 DEG C of dry 6h in drying box, obtains band after alternately being cleaned 5 times using the ethyl alcohol of deionized water and 95%
The nickel foam of NiSe active materials；
Step 4：The nickel foam for the active material of growth that step 3 is obtained is as upper/lower electrode, in accordance with the order from top to bottom
Nickel foam with NiSe active materials, diaphragm and nickel foam with NiSe active materials are stacked, electrolyte is then injected into,
Air locking is to get to the flexible super capacitor.
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| CN108511675B (en) * | 2018-04-13 | 2021-02-19 | 武汉理工大学 | Preparation method of flexible electrode material of lithium ion battery |
| CN110136975B (en) * | 2019-05-13 | 2021-01-05 | 华侨大学 | Preparation method and application of amorphous cobalt tetrathiomolybdate/nickel selenide nanosheet array composite material |
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| CN102324321A (en) * | 2011-08-26 | 2012-01-18 | 吉林大学 | Metallic nickel oxide/carbon composite electrode material carried by nickel foam substrate |
| CN102426925A (en) * | 2012-01-04 | 2012-04-25 | 黑龙江大学 | Method for preparing cobalt and zinc doped nickel hydroxide composite electrode material through electrodeposition |
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| CN102324321A (en) * | 2011-08-26 | 2012-01-18 | 吉林大学 | Metallic nickel oxide/carbon composite electrode material carried by nickel foam substrate |
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