CN108666148A - A kind of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials and preparation method thereof - Google Patents
A kind of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials and preparation method thereof Download PDFInfo
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- CN108666148A CN108666148A CN201810419397.6A CN201810419397A CN108666148A CN 108666148 A CN108666148 A CN 108666148A CN 201810419397 A CN201810419397 A CN 201810419397A CN 108666148 A CN108666148 A CN 108666148A
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- H—ELECTRICITY
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- 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
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- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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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
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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
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Abstract
The invention discloses a kind of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials and preparation method thereof.The present invention prepares Co salt and Al mixed salt solutions first, and urea is added and ammonium fluoride is stirred mixing, then immerses in above-mentioned mixed solution processed carbon cloth, obtains being supported on the CoAl hydroxide on carbon cloth by hydro-thermal reaction；The CoAl hydroxide being supported on carbon cloth is finally immersed progress soak at room temperature in 0.1 0.3mol/L sodium hydroxide solutions to etch to obtain combination electrode material.The present invention, which obtains porous C oAl double-metal hydroxide@carbon cloths combination electrode material, not only has good specific capacitance value, good cycling stability, and the high mechanical strength of electrode material and flexibility are good.There is certain development to be oriented to intelligent, convenient, the light and flexible electronic product that modern science and technology is constantly explored, is one of the energy and material of great future development future.
Description
Technical field
The invention belongs to material chemistry technical fields, are related to a kind of porous structure combination electrode material, it particularly relates to
A kind of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials and preparation method thereof.
Background technology
In the epoch of this science and technology rapid development of 21 century, living standards of the people step up, while the environment brought is asked
Topic also can not be ignored.With fossil energy exhaustion and problem of environmental pollution aggravation, people continuously search for new energy with
Replace traditional fossil energy.Electric energy is undoubtedly optimal selection, is the clean energy resource being most widely used in many energy storage devices
One of.In the society of this electronic product in length and breadth, we can not imagine the reality of not electrochemical energy storage system, and one does not have intelligence
Can the electronic portable devices such as mobile phone, laptop or iPod the world, also no electric vehicle, aircraft and other many can make
Our life is easier and more comfortable invention.In the world of this dependence energy, the electrochemical appliance for energy storage exists
Vital effect is played in terms of overcoming fossil fuel exhaustion.In various electrochemical energy storage devices, ultracapacitor by
Cause great interest in this Ji Nian academia in the performance of its superior power density, fast charging and discharging.
The increasingly miniaturization and flexibility of electronic device require energy storage device that must have lightweight, flexibility, and can have
Limit farthest plays high electrochemical performance in space.Therefore, seek the flexible energy storage device with high volume ratio performance at
For key.Flexible super capacitor is because it gets more and more people's extensive concerning with high power density and long life, as heat
The carbon material of point has many advantages, such as that high-specific surface area, low cost, chemical stability and thermal stability are high and conductivity is higher, but
Be its pore structure be difficult to control, energy density it is relatively low.And the transition metal oxide in fake capacitance electrode material has height
Theoretical specific capacity causes great concern.Chemical stability and energy density in order to balance, people usually will be with high conductivity
Carbon material and transition metal oxide with height ratio capacity are compound, to obtain ideal chemical property.
Invention content
In view of the above technical problems, the purpose of the present invention is to provide a kind of porous C oAl double-metal hydroxides@carbon cloths
Combination electrode material and preparation method thereof.This method is easy to operate, environmental-friendly, obtained porous C oAl bimetal hydroxides
Object@carbon cloths combination electrode material can solve the shortcomings of bad bimetallic oxide electric conductivity in the prior art, easy reunion, together
When the combination electrode material have good cyclical stability and mechanical flexibility.
The present invention obtains the mixed solution containing CoAl by being mixed first；Then processed carbon cloth is immersed mixed
It closes in solution and carries out hydro-thermal reaction, be down to room temperature naturally, place baking oven drying；It is finally immersed in NaOH solution and performs etching；
Supersound washing, drying obtain porous C oAl double-metal hydroxide@carbon cloth combination electrode materials.Specific technical solution of the present invention is situated between
It continues as follows.
The present invention provides a kind of preparation method of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials, specifically
Steps are as follows：
(1) CoAl double-metal hydroxides are prepared
First, at ambient temperature, by cobalt nitrate, aluminum nitrate element and deionized water ultrasonic mixing, it is made fully to dissolve, so
Urea is added afterwards and ammonium fluoride is stirred, obtains CoAl double-metal hydroxide mixed solutions；
(2) synthesis is supported on the combination electrode material on carbon cloth
After pretreated carbon cloth is immersed in CoAl double-metal hydroxide mixed solutions, hydro-thermal reaction, reaction are carried out
After, carbon cloth, supersound washing, drying are taken out, then immerse room temperature in the NaOH solution that molar concentration is 0.1-0.3mol/L and soak
Bubble etching 0.5-12h, obtains porous C oAl double-metal hydroxide@carbon cloth combination electrode materials.
In the present invention, in step (1), the molar ratio of cobalt nitrate and aluminum nitrate is 1:1~6:1, cobalt nitrate and deionized water
Mass volume ratio be 1:1~25:1mg/ml, ultrasonic mixing time are 20~30min.
In the present invention, in step (1), the molar ratio of cobalt nitrate and aluminum nitrate is 1:1~2:1, aluminum nitrate and deionized water
Mass volume ratio be 2:1~15:1mg/ml.
In the present invention, in step (1), the mass ratio of cobalt nitrate and urea is 1:1~1:5.
In the present invention, in step (1), the mass ratio of cobalt nitrate and ammonium fluoride is 3:1~8:1, mixing time be 20~
30min。
It is as follows to the pretreated method of carbon cloth in step (2) in the present invention：Carbon cloth size needed for first cutting, then successively
With deionized water, acetone, ethyl alcohol and deionized water supersound washing, finally it is dried in vacuo.
In the present invention, in step (2), carbon cloth area is 1*1~4*4cm2, hydrothermal temperature is 90~140 DEG C, reaction
Time be 12~for 24 hours.
In the present invention, in step (2), drying temperature is 50-60 DEG C, and drying time is 12~18h.
In the present invention, in step (2), the soak at room temperature etch period of NaOH solution is 5~10h.
The present invention also provides a kind of porous C oAl double-metal hydroxide@carbon cloth combination electrodes that above-mentioned preparation method obtains
Material.
Compared to the prior art, the beneficial effects of the present invention are：
The porous C oAl double-metal hydroxide@carbon cloth combination electrode materials that method through the invention obtains make full use of
Synergistic effect between bimetallic oxide, overcomes single metal oxide poor circulation, independent carbon material energy close
Spend low disadvantage, gained combination electrode material not only good cycling stability, mechanical flexibility is strong, and morphology controllable is strong, tool
There is higher specific capacitance, is one of ideal energy and material.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of simple carbon cloth in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of load C oAl hydroxide on carbon cloth in embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph that electrode material of the back loading on carbon cloth is etched in embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph that electrode material of the back loading on carbon cloth is etched in embodiment 2.
Fig. 5 is the scanning electron microscope (SEM) photograph that electrode material of the back loading on carbon cloth is etched in embodiment 3.
Fig. 6 is the porous C oAl double-metal hydroxide@carbon cloth combination electrode material cyclical stabilities of gained in embodiment 3
It can figure.
Fig. 7 is the transmission electron microscope picture that electrode material of the back loading on carbon cloth is etched in embodiment 3.
Fig. 8 is the X-ray diffraction pattern of gained porous C oAl double-metal hydroxide@carbon cloth powder in embodiment 3.
Fig. 9 is that porous CoAl double-metal hydroxides carbon cloth combination electrode material filling under constant current is obtained in embodiment 3
Discharge performance figure.
Figure 10 is the scanning electron microscope (SEM) photograph that electrode material of the back loading on carbon cloth is etched in embodiment 4.
Specific implementation mode
It is expanded on further below by specific embodiment and in conjunction with attached drawing to the present invention, but is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials, includes the following steps：
(1) pretreatment of carbon cloth
A. carbon cloth is cut into 2*2cm2Shape, use deionized water, acetone, ethyl alcohol, deionized water supersound washing each successively
15min, then be washed with deionized 2 times (mass percent concentration of the acetone be 60~98%, ethyl alcohol be anhydrous second
Alcohol)；
B. then 12h is dried in vacuo under the conditions of 60 DEG C.
(2) CoAl hydroxide is prepared
A. first, at room temperature, according to mass ratio, 150mg cobalt nitrates and 120mg aluminum nitrates are added to the burning of 200ml
In cup, and 80ml deionized waters are added to the inside, magnetic agitation 20min is to being mixed thoroughly；
B. 150mg urea, 40mg ammonium fluorides are then added in above-mentioned solution, magnetic agitation 20min is obtained to being uniformly mixed
To the double-metal hydroxide mixed solution containing CoAl.
(3) porous C oAl double-metal hydroxide@carbon cloth combination electrode materials are prepared
A. first, at room temperature, above-mentioned mixed solution is moved into polytetrafluoroethyllining lining stainless steel autoclave；And
The carbon cloth that step 1) pretreatment obtains tiltedly is put in a kettle, 90 DEG C of oven reaction 12h are put into after tightening；
B. after reaction, cooled to room temperature is washed 3 times with deionized water, EtOH Sonicate respectively, in 60 DEG C of conditions
Lower vacuum drying 12h；
C. the NaOH solution that 100ml molar concentrations are 0.1mol/L will be immersed with the carbon cloth of CoAl double-metal hydroxides
In carry out immersion 6h；
D. supersound washing is then carried out, dry 12h, obtains porous C oAl double-metal hydroxide@carbon under the conditions of 60 DEG C
Cloth combination electrode material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to the single carbon cloth of above-mentioned gained
It is scanned, the scanning electron microscope (SEM) photograph of gained is miscellaneous without other as shown in Figure 1, as can be seen from Figure 1 carbon cloth fiber surface is smooth
Matter is easy to metal loaded material.And the CoAl double-metal hydroxides powder to being supported on carbon cloth (without under etching condition)
It is scanned, gained scanning electron microscope (SEM) photograph by its sectional view as shown in Fig. 2, can be seen that CoAl hydroxide has successfully been born
Carbon cloth surfaces are loaded in, CoAl hydroxide is about made of the nanometer sheet of 10nm thickness.Fig. 3 is to be in 100ml molar concentrations
The porous C oAl double-metal hydroxide@carbon cloth combination electrode material powder electron microscopes of 6h are etched in 0.1mol/L NaOH solutions,
As can be seen from the figure partial etching falls aluminium hydroxide, obtains porous cobalt aluminium hydroxide uniform load on carbon cloth.
Electrochemical property test：
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrodes, and reference electrode is Ag/AgCl electrodes, work
The Pt nets of carrying active substance as electrode, with three-electrode system electrochemical workstation and blue electric system test material electrification
Learn performance.The results show that the combination electrode material prepared is in 1Ag-1Charging and discharging curve under galvanostatic conditions at symmetrical triangular shape,
Show good fake capacitance behavior.It is 1Ag in electric current-1It sweeps in the stable circulation linearity curve under speed, the specific capacity variation of material
Less, after 5000 cycles, specific capacity is still positively retained at 76% or so, protrudes it with good cyclical stability.
Embodiment 2
A kind of preparation method of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials, includes the following steps：
(1) pretreatment of carbon cloth
A. carbon cloth is cut into 2.5*2.5cm2Shape, washed successively with deionized water, acetone, ethyl alcohol, deionized water ultrasound
Wash each 15min, then be washed with deionized 2 times (mass percent concentration of the acetone be 60~98%, ethyl alcohol be it is anhydrous
Ethyl alcohol)；
B. then 12h is dried in vacuo under the conditions of 60 DEG C.
(2) CoAl hydroxide is prepared
A. first, at room temperature, according to mass ratio, 200mg cobalt nitrates and 150mg aluminum nitrates are added to the burning of 200ml
In cup, and 120ml deionized waters are added to the inside, magnetic agitation 20min is to being mixed thoroughly；
B. 300mg urea, 50mg ammonium fluorides are then added in above-mentioned solution, magnetic agitation 20min is obtained to being uniformly mixed
To the double-metal hydroxide mixed solution containing CoAl.
(3) porous C oAl double-metal hydroxide@carbon cloth combination electrode materials are prepared
A. first, at room temperature, above-mentioned mixed solution is moved into polytetrafluoroethyllining lining stainless steel autoclave；And
The carbon cloth that step 1) pretreatment obtains tiltedly is put in a kettle, 100 DEG C of oven reaction 18h are put into after tightening；
B. after reaction, cooled to room temperature is washed 3 times with deionized water, EtOH Sonicate respectively, in 60 DEG C of conditions
Lower vacuum drying 12h；
C. the NaOH solution that 120ml molar concentrations are 0.2mol/L will be immersed with the carbon cloth of CoAl double-metal hydroxides
In carry out immersion 8h；
D. supersound washing is then carried out, dry 14h, obtains porous C oAl double-metal hydroxide@carbon under the conditions of 60 DEG C
Cloth combination electrode material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned hole CoAl bimetallic hydrogen
Oxide@carbon cloth combination electrode material powder is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in Figure 4.Fig. 4 is rubbed in 120ml
The Electronic Speculum high magnification map of 8h is etched in your a concentration of 0.2mol/L NaoH solution, is significantly obtained it can be seen that etching in figure
Cobalt hydroxide uniform load on carbon cloth fiber, cellular is presented, is conducive to electrolyte well into further increasing electrode material
The capacitive character of material.
Electrochemical property test method is with embodiment 1, and under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt
Electrode, reference electrode are Ag/AgCl electrodes, and working electrode is the Pt nets of carrying active substance, with three-electrode system in electrochemistry
The chemical property of work station and blue electric system test material.The results show that the combination electrode material prepared is in 1Ag-1Constant current
Under the conditions of charging and discharging curve at symmetrical triangular shape, show good fake capacitance behavior, electric current be 1Ag-1Sweep following under speed
In ring stability curve, the specific capacity variation of material is little, and after 5000 cycles, specific capacity is still positively retained at 80% left side
The right side protrudes it with good cyclical stability.
Embodiment 3
A kind of preparation method of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials, includes the following steps：
(1) pretreatment of carbon cloth
A. carbon cloth is cut into 2*2cm2Shape, use deionized water, acetone, ethyl alcohol, deionized water supersound washing each successively
15min, then be washed with deionized 2 times (mass percent concentration of the acetone be 60~98%, ethyl alcohol be anhydrous second
Alcohol)；
B. then 12h is dried in vacuo under the conditions of 60 DEG C.
(2) CoAl hydroxide is prepared
A. first, at room temperature, according to mass ratio, 260mg cobalt nitrates and 160mg aluminum nitrates are added to the burning of 200ml
In cup, and 120ml deionized waters are added to the inside, magnetic agitation 30min is to being mixed thoroughly；
B. 400mg urea, 60mg ammonium fluorides are then added in above-mentioned solution, magnetic agitation 30min is obtained to being uniformly mixed
To the double-metal hydroxide mixed solution containing CoAl.
(3) porous C oAl double-metal hydroxide@carbon cloth combination electrode materials are prepared
A. first, at room temperature, above-mentioned mixed solution is moved into polytetrafluoroethyllining lining stainless steel autoclave；And
The carbon cloth that step 1) pretreatment obtains tiltedly is put in a kettle, 110 DEG C of oven reaction 19h are put into after tightening；
B. after reaction, cooled to room temperature is washed 3 times with deionized water, EtOH Sonicate respectively, in 60 DEG C of conditions
Lower vacuum drying 12h；
C. the NaOH solution that 150ml molar concentrations are 1.0mol/L will be immersed with the carbon cloth of CoAl double-metal hydroxides
In carry out immersion 9h；
D. supersound washing is then carried out, dry 16h, obtains porous C oAl double-metal hydroxide@carbon under the conditions of 60 DEG C
Cloth combination electrode material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned hole CoAl bimetallic hydrogen
Oxide@carbon cloth combination electrode material powder is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in Figure 5.Fig. 5 is rubbed in 100ml
The electron microscope that 9h is etched in your a concentration of 1.0mol/L NaoH solution, as can be seen from the figure successfully etches away hydroxide
Aluminium, obtains that cobalt hydroxide is poroid and uniform load is on carbon cloth fiber.It is 1.0mol/LNaoH that Fig. 7, which is in 150ml molar concentrations,
The transmission electron microscope picture under the conditions of 9h is etched in solution, it can be seen that the spacing of lattice of the combination electrode material of preparation is about
0.8nm corresponds to (003) face, and is evenly distributed, and Fig. 8 is porous C oAl double-metal hydroxide@carbon cloth combination electrode material powder
End XRD diagram, as can be seen from the figure there is strong peak at 2 θ=11.528,23.205,38.783, correspond respectively to (003),
(006), the diffraction lattice in (015) face shows that the combination electrode material prepared contains Co6Al2CO3(OH)16·4H2O is typical
Hydrotalcite type structure, corresponding chemical property significantly improves.
Electrochemical property test：
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrodes, and reference electrode is Ag/AgCl electrodes, work
The Pt nets of carrying active substance as electrode, with three-electrode system electrochemical workstation and blue electric system test material electrification
Learn performance.Fig. 9 is the combination electrode material of preparation in 1Ag-1Charging and discharging curve under galvanostatic conditions is at symmetrical triangular shape, performance
Go out good fake capacitance behavior.Material of the present invention is as shown in fig. 6, be 1Ag in electric current-1It sweeps in the stable circulation linearity curve under speed,
The specific capacity variation of material is little, and after 5000 cycles, specific capacity is still positively retained at 96% or so, protrudes it with good
Good cyclical stability.
Embodiment 4
A kind of preparation method of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials, includes the following steps：
(1) pretreatment of carbon cloth
A. carbon cloth is cut into 2*2cm2Shape, use deionized water, acetone, ethyl alcohol, deionized water supersound washing each successively
15min, then be washed with deionized 2 times (mass percent concentration of the acetone be 60~98%, ethyl alcohol be anhydrous second
Alcohol)；
B. then 12h is dried in vacuo under the conditions of 60 DEG C.
(2) CoAl hydroxide is prepared
A. first, at room temperature, according to mass ratio, 300mg cobalt nitrates and 200mg aluminum nitrates are added to the burning of 500ml
In cup, and 180ml deionized waters are added to the inside, magnetic agitation 30min is to being mixed thoroughly；
B. 420mg urea, 80mg ammonium fluorides are then added in above-mentioned solution, magnetic agitation 30min is obtained to being uniformly mixed
To the double-metal hydroxide mixed solution containing CoAl.
(3) porous C oAl double-metal hydroxide@carbon cloth combination electrode materials are prepared
A. first, at room temperature, above-mentioned mixed solution is moved into polytetrafluoroethyllining lining stainless steel autoclave；And
The carbon cloth that step 1) pretreatment obtains tiltedly is put in a kettle, 120 DEG C of oven reaction 20h are put into after tightening；
B. after reaction, cooled to room temperature is washed 3 times with deionized water, EtOH Sonicate respectively, in 60 DEG C of conditions
Lower vacuum drying 12h；
C. the NaOH solution that 180ml molar concentrations are 4.0mol/L will be immersed with the carbon cloth of CoAl double-metal hydroxides
In carry out immersion 10h；
D. supersound washing is then carried out, dry 16h, obtains porous C oAl double-metal hydroxide@carbon under the conditions of 60 DEG C
Cloth combination electrode material.
Using Flied emission scanning transmission electron microscope (German Libra 120) instrument, to the porous C oAl of above-mentioned gained
Double-metal hydroxide@carbon cloth combination electrode materials are scanned figure, and it is 4.0mol/L that Figure 10, which is in 180ml molar concentrations,
The electron microscope that 12h is etched in NaOH solution, it can be seen from the figure that there is crack phenomenon in material, illustrate but concentration it is excessive and
Overlong time is to preparing the influence of electrode material.
Electrochemical property test method is with embodiment 1, and under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt
Electrode, reference electrode are Ag/AgCl electrodes, and working electrode is the Pt nets of carrying active substance, with three-electrode system in electrochemistry
The chemical property of work station and blue electric system test material.It is 1Ag in electric current-1It sweeps in the stable circulation linearity curve under speed, material
The specific capacity variation of material is little, and after 5000 cycles, specific capacity is maintained at 65% or so, shows to etch concentration and time
Influence to electrode material, causes electrode material to be broken, and cyclical stability is substantially reduced.
In conclusion a kind of preparation side of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials of the present invention
Method, charge-discharge performance, cyclical stability and the scanning electron microscope performance map of each embodiment of Integrated comparative, the electricity prepared by embodiment 3
Chemical property is best, and porous C oAl double-metal hydroxide@carbon cloth combination electrodes are in 1Ag‐1Have when constant current charge-discharge
786.4Fg‐1Specific capacity there remains nearly 96% specific capacity after cycle 5000 times, prominent its has to follow well
Ring stability makes full use of the synergistic effect of carbon material and transition metal oxide, prepares that chemical property is good and machine
The flexible combination electrode material of tool.
Composite material of the present invention makes full use of the spy that carbon cloth stability is strong, good conductivity and bimetallic oxide specific capacity are high
Point fully utilizes the synergistic effect of the two, overcomes the shortcomings of single metal material well.
The above is only that the specific of embodiments of the present invention is enumerated, and appoints made by technical solution according to the present invention
What equivalent transformation, is within the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials, which is characterized in that specific step
It is rapid as follows：
(1) CoAl double-metal hydroxides are prepared
First, at ambient temperature, by cobalt nitrate, aluminum nitrate element and deionized water ultrasonic mixing, so that it is fully dissolved, then add
Enter urea and ammonium fluoride is stirred, obtains CoAl double-metal hydroxide mixed solutions；
(2) synthesis is supported on the combination electrode material on carbon cloth
After pretreated carbon cloth is immersed in CoAl double-metal hydroxide mixed solutions, hydro-thermal reaction is carried out, reaction terminates
Afterwards, carbon cloth, supersound washing, drying are taken out, then immerses soak at room temperature in the NaOH solution that molar concentration is 0.1-0.3mol/L and carves
0.5-12h is lost, porous C oAl double-metal hydroxide@carbon cloth combination electrode materials are obtained.
2. preparation method according to claim 1, which is characterized in that in step (1), the molar ratio of cobalt nitrate and aluminum nitrate
It is 1:1~6:1, the mass volume ratio of cobalt nitrate and deionized water is 1:1~25:1mg/ml, the ultrasonic mixing time be 20~
30min。
3. preparation method according to claim 1, which is characterized in that in step (1), the molar ratio of cobalt nitrate and aluminum nitrate
It is 1:1~2:1, the mass volume ratio of aluminum nitrate and deionized water is 2:1~15:1mg/ml.
4. preparation method according to claim 1, which is characterized in that in step (1), the mass ratio of cobalt nitrate and urea is
1:1~1:5.
5. preparation method according to claim 1, which is characterized in that in step (1), the mass ratio of cobalt nitrate and ammonium fluoride
It is 3:1~8:1, mixing time is 20~30min.
6. preparation method according to claim 1, which is characterized in that in step (2), such as to the pretreated method of carbon cloth
Under：Carbon cloth size needed for first cutting, then uses deionized water, acetone, ethyl alcohol and deionized water supersound washing, last vacuum successively
It is dry.
7. preparation method according to claim 1, which is characterized in that in step (2), carbon cloth area is 1*1~4*4cm2,
Hydrothermal temperature be 90~140 DEG C, the reaction time be 12~for 24 hours.
8. preparation method according to claim 1, which is characterized in that in step (2), drying temperature is 50-60 DEG C, drying
Time is 12~18h.
9. preparation method according to claim 1, which is characterized in that in step (2), soak at room temperature etch period be 5~
10h。
10. the porous C oAl double-metal hydroxide@carbon cloths that a kind of preparation method as described in one of claim 1-9 obtains are multiple
Composite electrode material.
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| CN109772336A (en) * | 2019-03-05 | 2019-05-21 | 浙江工业大学 | A kind of porous double-metal hydroxide catalyst and its preparation method and application for the oxidation of electro-catalysis alcohols selectivity |
| CN110010359A (en) * | 2019-04-19 | 2019-07-12 | 南昌航空大学 | A kind of preparation method of nickel cobalt/hydroxide combination electrode material |
| CN110379639A (en) * | 2019-07-02 | 2019-10-25 | 安徽师范大学 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
| CN111508718A (en) * | 2020-04-01 | 2020-08-07 | 安徽师范大学 | Co2Al/Co2Mn electrode composite material and preparation method thereof |
| CN111564324A (en) * | 2020-06-28 | 2020-08-21 | 电子科技大学 | Preparation method of carbon cloth @ sheet cobalt-aluminum hydrotalcite flexible electrode |
| CN115142084A (en) * | 2022-06-21 | 2022-10-04 | 江汉大学 | Self-supporting metal-hydrotalcite-like compound composite catalytic electrode and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103426649A (en) * | 2013-08-21 | 2013-12-04 | 吉林大学 | Preparation method for different carbon fibers / cobalt hydroxide electrode and solid-liquid composite electrode system |
| CN107195471A (en) * | 2017-06-01 | 2017-09-22 | 上海应用技术大学 | A kind of preparation method of the Ni-based combination electrode materials of porous C oAl@ |
-
2018
- 2018-05-04 CN CN201810419397.6A patent/CN108666148A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103426649A (en) * | 2013-08-21 | 2013-12-04 | 吉林大学 | Preparation method for different carbon fibers / cobalt hydroxide electrode and solid-liquid composite electrode system |
| CN107195471A (en) * | 2017-06-01 | 2017-09-22 | 上海应用技术大学 | A kind of preparation method of the Ni-based combination electrode materials of porous C oAl@ |
Non-Patent Citations (2)
| Title |
|---|
| DUO WANG,ET AL.: ""Layered Co–Mn hydroxide nanoflakes grown on carbon cloth as binder-free flexible electrodes for supercapacitors"", 《J MATER SCI》 * |
| 郑晓宇: ""三维Ni-Co羟基氧化物电极材料的原位活化及其性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772336A (en) * | 2019-03-05 | 2019-05-21 | 浙江工业大学 | A kind of porous double-metal hydroxide catalyst and its preparation method and application for the oxidation of electro-catalysis alcohols selectivity |
| CN110010359A (en) * | 2019-04-19 | 2019-07-12 | 南昌航空大学 | A kind of preparation method of nickel cobalt/hydroxide combination electrode material |
| CN110379639A (en) * | 2019-07-02 | 2019-10-25 | 安徽师范大学 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
| CN111508718A (en) * | 2020-04-01 | 2020-08-07 | 安徽师范大学 | Co2Al/Co2Mn electrode composite material and preparation method thereof |
| CN111564324A (en) * | 2020-06-28 | 2020-08-21 | 电子科技大学 | Preparation method of carbon cloth @ sheet cobalt-aluminum hydrotalcite flexible electrode |
| CN111564324B (en) * | 2020-06-28 | 2022-06-14 | 电子科技大学 | Preparation method of carbon cloth @ sheet cobalt-aluminum hydrotalcite flexible electrode |
| CN115142084A (en) * | 2022-06-21 | 2022-10-04 | 江汉大学 | Self-supporting metal-hydrotalcite-like compound composite catalytic electrode and preparation method and application thereof |
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