CN107346709A - Preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor and products thereof - Google Patents
Preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor and products thereof Download PDFInfo
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- CN107346709A CN107346709A CN201710793132.8A CN201710793132A CN107346709A CN 107346709 A CN107346709 A CN 107346709A CN 201710793132 A CN201710793132 A CN 201710793132A CN 107346709 A CN107346709 A CN 107346709A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 17
- 239000010941 cobalt Substances 0.000 title claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 20
- 241000257465 Echinoidea Species 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- 239000002086 nanomaterial Substances 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 12
- 230000008014 freezing Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004108 freeze drying Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 14
- 238000001354 calcination Methods 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 235000015165 citric acid Nutrition 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor and products thereof, including prepared by positive pole, prepared by negative pole and assembling ultracapacitor.Positive electrode is to prepare NiCo by hydro-thermal method2O4Sea urchin shape material, Ni and Co and multiple valence states be present so that it, which has, is higher than Co3O4With NiO electro-chemical activity, and there is synergy simultaneously；Negative pole is to prepare the three-dimensional porous carbon of loose structure by freeze-drying, and carbon material skeleton structure possesses good electric conductivity, and the hole of carbon material has good electrolyte wellability, can improve specific capacitance.Positive and negative pole material is subjected to smear afterwards and is assembled into Asymmetric Supercapacitor.The present invention is by preparing Ni nanoparticle Co2O4Positive electrode and porous carbon negative pole material assembling Asymmetric Supercapacitor, improve window voltage and add fake capacitance, improve the energy density of ultracapacitor.
Description
Technical field
The invention belongs to electrochemical capacitor technical field, especially a kind of cobalt acid nickel/three-dimensional porous carbon is asymmetric super
Preparation method of capacitor and products thereof.
Background technology
Under the background of environment and the getting worse of energy problem, it is increasingly urgent to find green energy storage device,
Ultracapacitor causes the extensive concern of people in the case of this.Ultracapacitor also known as electrochemical capacitor, be it is a kind of between
A kind of novel energy-storing element between ordinary capacitor and battery, it possesses discharge power as traditional capacitance, also possessing
The ability of battery reserve electric charge is learned, has filled up blank between the two.It has that power density is big, has extended cycle life, be green
The characteristics of, but it also has the low fatal defects of energy density, so as to cause the ultracapacitor with battery equal energy density to have
Very big volume and weight, is unfavorable for its extensive use.Therefore numerous scholars be directed to improve ultracapacitor energy it is close
Degree.
Electrochemical capacitor can be divided into：1. double layer capacitor, high-specific surface area carbon material mainly is used, is to be based on carbon
Electric double layer capacitance caused by the separation of electrode/electrolyte interface charge；2. pseudocapacitors, mainly using metal oxide as electricity
Pole, the caused adsorption capacitance using the redox reaction occurred in oxide electrode material surface and body phase.It is no matter above-mentioned
Which kind of ultracapacitor, its energy density are far below battery, turn into the bottleneck for limiting it in energy storage field large-scale application,
Therefore the energy density for improving ultracapacitor is just particularly important.
Formula E=0.5CV is calculated according to energy density2It can be seen that want to improve energy density E, first, improving window electricity
V is pressed, second, improving the specific capacitance C of electrode material.There are other scholars by using organic electrolyte to improve window voltage, still
Because the high pollution of organic electrolyte is unfavorable for the extensive use of ultracapacitor.The another aspect for widening window voltage is exactly
Construct the Asymmetric Supercapacitor such as A of CN 103258656 and disclose a kind of Asymmetric Supercapacitor electricity based on nickel foam
The preparation method of pole；The A of CN 103871752 disclose a kind of copper-based asymmetric type supercapacitor of oxidation and preparation method thereof.
Negative material has scholar to be sintered to prepare high-specific surface area carbon material, such as using the pore structure direct activation of biomass matrix script
The A of CN 104891491 disclose a kind of preparation method of ultracapacitor with bamboo shoots based active carbon；The A of CN 104843685 are public
A kind of method that porous class graphene carbon electrode material is prepared using excrement of animals as raw material is opened.But the pore structure of this method is not
It can effectively control, the hole of biomass script can only be relied on.
The content of the invention
The present invention proposes a kind of preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor and products thereof,
Electrode material is prepared by the method for simple economy, so as to assemble the ultracapacitor of high-energy-density.
The present invention will be achieved by the following technical programs：A kind of cobalt acid nickel/asymmetric super capacitor of three-dimensional porous carbon
The preparation method of device, comprises the following steps：
(1) NiCo is prepared2O4Nano material：By soluble nickel salt：Soluble cobaltatess：Urea in molar ratio 1:2：10~
100 ultrasonic disperses stir 1h~4h in deionized water, after be put into hydrothermal reaction kettle 120 DEG C~180 DEG C reaction 6h~12h,
It is to be cooled to room temperature carry out filtering and washing after, under the conditions of 100 DEG C~150 DEG C dry 2h~8h, after 200 are calcined in tube furnace
DEG C~500 DEG C, 2h~8h, 1 DEG C/min of programming rate, obtain NiCo2O4Nano material；
(2) NiCo is prepared2O4Nano material positive pole：By NiCo2O4Nano material, carbon black, PTFE in mass ratio 8：1：1 is mixed
Magnetic agitation 4h~10h is closed into slurry, after slurry is coated in nickel foam, 60 DEG C~100 DEG C drying 2h~8h, be pressed into thin slice,
Vacuum drying obtains NiCo again2O4Nano material positive pole；
(3) porous carbon materials are prepared：By citric acid, sodium chloride or sodium sulphate dissolving in deionized water stir 20h~
48h, after be put into reaction utensil freezing 12h~48h until freezing is complete, then is put in freeze-drying 24h~48h shapes in freeze drier
Into white powder, after white powder be put in tube furnace lead to protection gas, calcine 2h~6h at 700~800 DEG C, finally washing is taken out
Dried after filter, obtaining porous carbon materials；
(4) porous carbon materials negative pole is prepared：By porous carbon materials, carbon black, PTFE in mass ratio 8：1：1 mixing magnetic agitation
4h~10h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains porous carbon materials negative pole；
(5) ultracapacitor is assembled：The NiCo that step (2) is obtained2O4Nano material positive pole and step (4) obtain more
Hole carbon material negative pole is separated with barrier film, instills electrolyte, button cell is assembled into positive pole pad, negative pole pad, packaged, i.e.,
For Asymmetric Supercapacitor.
Soluble nickel salt is Ni (NO in the step (1)3)2·6H2O, soluble cobaltatess are Co (NO3)2·6H2O。
Citric acid in the step (3)：Sodium chloride or sodium sulphate are 1 in molar ratio：25.
Protection gas is H in the step (3)2、N2, one or more combination in Ar.
Step (5) electrolyte is aqueous electrolyte, and concentration is (2~6) mol/L.
The electrolyte is KOH solution.
Cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor that above-mentioned preparation method obtains.
The positive electrode is sea urchin shape, and negative material is three-dimensional porous carbon.
Beneficial effects of the present invention：
(1) the three-dimensional porous carbon negative pole material prepared possesses high specific surface area, and carbon material skeleton structure possesses good
Electric conductivity, the hole of carbon material have good electrolyte wellability, improve specific capacitance.
(2) bimetallic oxide electrode is used, two kinds of metals occur synergy, Ni and Co and multiple valencys be present
State so that it, which has, is higher than CO3O4With NiO electro-chemical activity.Other NiCo2O4In enrich pore passage structure add electrode
The contact area of material and electrolyte, improve the efficiency that active material participates in faraday's reaction.
(3) make asymmetric capacitor and expand potential window, an electrode uses three-dimensional porous carbon material, another electrode
Use NiCo2O4Material, because electrode asymmetry, potential window will improve.Because specific energy E=1/2CV2, so when electricity
Position window improves, and E can be by a square times growth.
Brief description of the drawings
Fig. 1 is the NiCo of embodiment 12O4SEM figure；
Fig. 2 is the NiCo of embodiment 22O4SEM figure；
Fig. 3 is the NiCo of embodiment 32O4SEM figure；
Fig. 4 is the NiCo of embodiment 42O4SEM figure；
Fig. 5 is the NiCo of embodiment 52O4SEM figure；
Fig. 6 is the NiCo of embodiment 62O4SEM figure；
Fig. 7 is the SEM figures of three-dimensional porous carbon in embodiment 1；
Fig. 8 is the NiCo of embodiment 12O4XRD spectra.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description：
The preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor of the present invention, comprises the following steps：
(1) NiCo is prepared2O4Nano material：By soluble nickel salt：Soluble cobaltatess：Urea in molar ratio 1:2：10~
100 ultrasonic disperses stir 1h~4h in deionized water, after be put into hydrothermal reaction kettle 120 DEG C~180 DEG C reaction 6h~12h,
It is to be cooled to room temperature carry out filtering and washing after, under the conditions of 100 DEG C~150 DEG C dry 2h~8h, after 200 are calcined in tube furnace
DEG C~500 DEG C, 2h~8h, 1 DEG C/min of programming rate, obtain NiCo2O4Nano material；
(2) NiCo is prepared2O4Nano material positive pole：By NiCo2O4Nano material, carbon black, PTFE in mass ratio 8：1：1 is mixed
Magnetic agitation 4h~10h is closed into slurry, after slurry is coated in nickel foam, 60 DEG C~100 DEG C drying 2h~8h, be pressed into thin slice,
Vacuum drying obtains NiCo again2O4Nano material positive pole；
(3) porous carbon materials are prepared：By citric acid, sodium chloride or sodium sulphate dissolving in deionized water stir 20h~
48h, after be put into reaction utensil freezing 12h~48h until freezing is complete, then is put in freeze-drying 24h~48h shapes in freeze drier
Into white powder, after white powder be put in tube furnace lead to protection gas, calcine 2h~6h at 700~800 DEG C, finally washing is taken out
Dried after filter, obtaining porous carbon materials；
(4) porous carbon materials negative pole is prepared：Porous carbon materials, carbon black, PTFE are mixed into magnetic agitation 4h~10h into slurry
Material, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains porous carbon materials negative pole；
(5) ultracapacitor is assembled：The NiCo that step (2) is obtained2O4Nano material positive pole and step (4) obtain more
Hole carbon material negative pole is separated with barrier film, instills electrolyte, button cell is assembled into positive pole pad, negative pole pad, packaged, i.e.,
For Asymmetric Supercapacitor.
Soluble nickel salt is Ni (NO in the step (1)3)2·6H2O, soluble cobaltatess are Co (NO3)2·6H2O。
Citric acid in the step (3)：Sodium chloride or sodium sulphate are 1 in molar ratio：25.
Protection gas is H in the step (3)2、N2, one or more combination in Ar.
Step (5) electrolyte is aqueous electrolyte, and concentration is (2~6) mol/L.
The electrolyte is KOH solution.
Cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor that above-mentioned preparation method obtains.
The positive electrode is sea urchin shape, and negative material is three-dimensional porous carbon.
In the present invention by building NiCo2O4/ three-dimensional porous carbon Asymmetric Supercapacitor improves window voltage.
In terms of the specific capacitance for improving electrode material, transition metal oxide or hydroxide are often made with for fake capacitance material,
Positive electrode uses NiCo in the present invention2O4Nano material, Ni and Co and multiple valence states be present so that it, which has, is higher than CO3O4
With NiO electro-chemical activity, acted synergistically so as to have；Negative material then by prepare using the carbon material of high-specific surface area come
Specific capacitance is improved, in the present invention by using the crystal structure of soluble salt, organic matter is freezed after effectively being mixed with soluble salt
Organic matter is set to be attached in the crystal structure of soluble salt, rear convection drying carbonization makes the crystal structure of organic matter holding organic matter,
So as to form similar pore structure, the specific capacitance C of ultracapacitor is improved, and then improves the energy density of ultracapacitor.
Embodiment 1
(1) by 0.29gNi (NO3)2·6H2O and 0.58gCo (NO3)2·6H2O and 0.6g urea is added to 35mL deionizations
1h is stirred in water, 120 DEG C of reaction 6h, question response kettle in homogeneous reaction stove are placed in thermal response of falling back kettle and returns back to room temperature,
Material in reactor is subjected to filtering and washing 3 times, the material that suction filtration obtains is put in baking oven and dries 3h at 120 DEG C, is obtained
Active material.Active material, carbon black, PTFE are mixed into magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying pressure
Flakiness, then vacuum drying obtain NiCo2O4(see Fig. 1) nano material positive pole.
(2) 2.5g citric acids and 20.89gNaCl are dissolved in magnetic agitation 24h in 70mL deionized waters, after will be stirred
Solution is put in big culture dish and freezes 24h, after by the culture dish after freezing be placed in freeze drier dry 24h obtain white powder
End, white powder is ground with agate mortar.White powder is placed in tube furnace in N again2、H2(flow-rate ratio 1:3) under atmosphere
750 DEG C of calcining 2h, then by the powder filtering and washing 5 times after calcining, dry 6h at 120 DEG C and obtain three-dimensional porous carbon.Three-dimensional is more
Hole carbon, carbon black, PTFE mix magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum is dried
It is dry to obtain three-dimensional porous carbon (see Fig. 7) material negative pole.
(3) take 33.6gKOH to be added in 100mL deionized waters, be completely dissolved, obtain 6mol/L KOH electrolyte.
(4) using pole piece obtained by step (1) and step (2) as anode pole piece and cathode pole piece, with positive pole pad,
Negative pole pad, barrier film are assembled into button cell apperance, instill electrolyte, packaged, as Asymmetric Supercapacitor.
Embodiment 2
(1) by 0.29gNi (NO3)2·6H2O and 0.58gCo (NO3)2·6H2O and 1.2g urea is added to 35mL deionizations
1h is stirred in water, 120 DEG C of reaction 9h, question response kettle in homogeneous reaction stove are placed in thermal response of falling back kettle and returns back to room temperature,
Material in reactor is subjected to filtering and washing 3 times, the material that suction filtration obtains is put in 100 DEG C of drying 6h in baking oven, obtains activity
Material.By active material, carbon black, PTFE in mass ratio 8：1：1 mixing magnetic agitation 4h into slurry, after slurry is coated in nickel foam
On, drying is pressed into thin slice, then vacuum drying obtains NiCo2O4(see Fig. 2) nano material positive pole.
(2) 2.5g citric acids and 20.89gNaCl are dissolved in magnetic agitation 30h in 70mL deionized waters, after will be stirred
Solution is put in big culture dish and freezes 36h, after by the culture dish after freezing be placed in freeze drier dry 36h obtain white powder
End, white powder is ground with agate mortar.White powder is placed in tube furnace in N again2、H2(flow-rate ratio 1:3) under atmosphere
720 DEG C of calcining 4h, then the powder filtering and washing 5 times after calcining, rear drying are obtained into three-dimensional porous carbon.By three-dimensional porous carbon, charcoal
Black, PTFE in mass ratio 8：1：1 mixing magnetic agitation 4h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then
Vacuum drying obtains three-dimensional porous carbon material negative pole.
(3) take 33.6gKOH to be added in 100mL deionized waters, be completely dissolved, obtain 6mol/LKOH electrolyte.
(4) using pole piece obtained by step (1) and step (2) as anode pole piece and cathode pole piece, with positive pole pad,
Negative pole pad, barrier film are assembled into button cell apperance, instill electrolyte, packaged, as Asymmetric Supercapacitor.
Embodiment 3
(1) by 0.29gNi (NO3)2·6H2O and 0.58gCo (NO3)2·6H2O and 6g urea is added to 35mL deionized waters
Middle stirring 2h, 150 DEG C of reaction 15h, question response kettle in homogeneous reaction stove are placed in thermal response of falling back kettle and returns back to room temperature, will
Material carries out filtering and washing 3 times in reactor, and the material that suction filtration obtains is put in 140 DEG C of drying 5h in being dried in baking oven, obtained
Active material.By active material, carbon black, PTFE in mass ratio 8：1：1 mixing magnetic agitation 8h into slurry, after slurry is coated in bubble
On foam nickel, drying is pressed into thin slice, then vacuum drying obtains NiCo2O4(see Fig. 3) nano material positive pole.
(2) 2.5g citric acids and 20.89gNaCl are dissolved in the night of magnetic agitation one in 70mL deionized waters, after will be stirred
Solution be put in big culture dish and freeze 30h, after the culture dish after freezing is placed in freeze drier dries 30h and obtain white
Powder, white powder is ground with agate mortar.White powder is placed in tube furnace in N again2、H2(flow-rate ratio 1:3) under atmosphere
780 DEG C of calcining 4h, then the powder filtering and washing 5 times after calcining, rear drying are obtained into three-dimensional porous carbon.By three-dimensional porous carbon, charcoal
Black, PTFE mixes magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains
Three-dimensional porous carbon material negative pole.
(3) take 33.6gKOH to be added in 100mL deionized waters, be completely dissolved, obtain 6mol/LKOH electrolyte.
(4) using pole piece obtained by step (1) and step (2) as anode pole piece and cathode pole piece, with positive pole pad,
Negative pole pad, barrier film are assembled into button cell apperance, instill electrolyte, packaged, as Asymmetric Supercapacitor.
Embodiment 4
(1) by 0.29gNi (NO3)2·6H2O and 0.58gCo (NO3)2·6H2O and 0.6g urea is added to 35mL deionizations
1h is stirred in water, 150 DEG C of reaction 9h, question response kettle in homogeneous reaction stove are placed in thermal response of falling back kettle and returns back to room temperature,
Material in reactor is subjected to filtering and washing 3 times, the material that suction filtration obtains is put in baking oven and dried, obtains active material.Will
Active material, carbon black, PTFE in mass ratio 8：1：1 mixing magnetic agitation 8h into slurry, after slurry is coated in nickel foam, dry
Thin slice is pressed into, then vacuum drying obtains NiCo2O4(see Fig. 4) nano material positive pole.
(2) 2.5g citric acids and 20.89gNaCl are dissolved in the night of magnetic agitation one in 70mL deionized waters, after will be stirred
Solution be put in big culture dish and freeze 24h, after the culture dish after freezing is placed in freeze drier dries 24h and obtain white
Powder, white powder is ground with agate mortar.White powder is placed in tube furnace in N again2、H2(flow-rate ratio 1:3) under atmosphere
750 DEG C of calcining 2h, then the powder filtering and washing 5 times after calcining, rear drying are obtained into three-dimensional porous carbon.By three-dimensional porous carbon, charcoal
Black, PTFE mixes magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains
Three-dimensional porous carbon material negative pole.
(3) take 33.6gKOH to be added in 100mL deionized waters, be completely dissolved, obtain 6mol/LKOH electrolyte.
(4) using pole piece obtained by step (1) and step (2) as anode pole piece and cathode pole piece, with positive pole pad,
Negative pole pad, barrier film are assembled into button cell apperance, instill electrolyte, packaged, as Asymmetric Supercapacitor.
Embodiment 5
(1) by 0.29gNi (NO3)2·6H2O and 0.58gCo (NO3)2·6H2O and 6g urea is added to 35mL deionized waters
Middle stirring 1h, 150 DEG C of reaction 6h, question response kettle in homogeneous reaction stove are placed in thermal response of falling back kettle and returns back to room temperature, will
Material carries out filtering and washing 3 times in reactor, and the material that suction filtration obtains is put in baking oven and dried, obtains active material.Will be living
Property material, carbon black, PTFE mix magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum
Drying obtains NiCo2O4(see Fig. 5) nano material positive pole.
(2) 2.5g citric acids and 20.89gNaCl are dissolved in the night of magnetic agitation one in 70mL deionized waters, after will be stirred
Solution be put in big culture dish and freeze 24h, after the culture dish after freezing is placed in freeze drier dries 24h and obtain white
Powder, white powder is ground with agate mortar.White powder is placed in tube furnace in N again2、H2(flow-rate ratio 1:3) under atmosphere
750 DEG C of calcining 2h, then the powder filtering and washing 5 times after calcining, rear drying are obtained into three-dimensional porous carbon.By three-dimensional porous carbon, charcoal
Black, PTFE mixes magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains
Three-dimensional porous carbon material negative pole.
(3) take 33.6gKOH to be added in 100mL deionized waters, be completely dissolved, obtain 6mol/LKOH electrolyte.
(4) using pole piece obtained by step (1) and step (2) as anode pole piece and cathode pole piece, with positive pole pad,
Negative pole pad, barrier film are assembled into button cell apperance, instill electrolyte, packaged, as Asymmetric Supercapacitor.
Embodiment 6
(1) by 0.29gNi (NO3)2·6H2O and 0.58gCo (NO3)2·6H2O and 0.6g urea is added to 35mL deionizations
1h is stirred in water, 180 DEG C of reaction 12h, question response kettle in homogeneous reaction stove are placed in thermal response of falling back kettle and returns back to room temperature,
Material in reactor is subjected to filtering and washing 3 times, the material that suction filtration obtains is put in baking oven and dried, obtains active material.Will
Active material, carbon black, PTFE mix magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then very
Sky drying obtains NiCo2O4(see Fig. 6) nano material positive pole.
(2) 2.5g citric acids and 20.89gNaCl are dissolved in the night of magnetic agitation one in 70mL deionized waters, after will be stirred
Solution be put in big culture dish and freeze 24h, after the culture dish after freezing is placed in freeze drier dries 24h and obtain white
Powder, white powder is ground with agate mortar.White powder is placed in tube furnace in N again2、H2(flow-rate ratio 1:3) under atmosphere
750 DEG C of calcining 2h, then the powder filtering and washing 5 times after calcining, rear drying are obtained into three-dimensional porous carbon.By three-dimensional porous carbon, charcoal
Black, PTFE mixes magnetic agitation 8h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains
Three-dimensional porous carbon material negative pole.
(3) take 33.6gKOH to be added in 100mL deionized waters, be completely dissolved, obtain 6mol/LKOH electrolyte.
(4) using pole piece obtained by step (1) and step (2) as anode pole piece and cathode pole piece, with positive pole pad,
Negative pole pad, barrier film are assembled into button cell apperance, instill electrolyte, packaged, as Asymmetric Supercapacitor.
In summary, present disclosure is not limited in the above embodiments, and the knowledgeable people in same area can
Can propose other embodiments easily within the technological guidance's thought of the present invention, but this embodiment is included in this hair
Within the scope of bright.
Claims (8)
1. a kind of preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor, it is characterised in that including following step
Suddenly：
(1) NiCo is prepared2O4Nano material：By soluble nickel salt：Soluble cobaltatess：Urea in molar ratio 1:2：10~100 surpass
Sound is scattered in deionized water stirring 1h~4h, after be put into hydrothermal reaction kettle 120 DEG C~180 DEG C reaction 6h~12h, it is to be cooled
To room temperature carry out filtering and washing after, under the conditions of 100 DEG C~150 DEG C dry 2h~8h, after in tube furnace calcine 200 DEG C~
500 DEG C, 2h~8h, 1 DEG C/min of programming rate, obtain NiCo2O4Nano material；
(2) NiCo is prepared2O4Nano material positive pole：By NiCo2O4Nano material, carbon black, PTFE in mass ratio 8：1：1 mixing magnetic force
4h~10h is stirred into slurry, after slurry is coated in nickel foam, 60 DEG C~100 DEG C drying 2h~8h, be pressed into thin slice, then vacuum
Drying obtains NiCo2O4Nano material positive pole；
(3) porous carbon materials are prepared：20h~48h is stirred into the dissolving of citric acid, sodium chloride or sodium sulphate in deionized water,
After be put into reaction utensil freezing 12h~48h until freezing is complete, then be put in freeze drier be freeze-dried 24h~48h formed it is white
Color powder, after by white powder be put in tube furnace lead to protection gas, 700~800 DEG C calcine 2h~6h, finally washing filter after
Drying, obtains porous carbon materials；
(4) porous carbon materials negative pole is prepared：By porous carbon materials, carbon black, PTFE in mass ratio 8：1：1 mixing magnetic agitation 4h~
10h into slurry, after slurry is coated in nickel foam, drying is pressed into thin slice, then vacuum drying obtains porous carbon materials negative pole；
(5) ultracapacitor is assembled：The NiCo that step (2) is obtained2O4The porous carbon that nano material positive pole and step (4) obtain
Material negative pole is separated with barrier film, instills electrolyte, button cell is assembled into positive pole pad, negative pole pad, packaged, as non-
Symmetrical ultracapacitor.
2. the preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor, its feature exist according to claim 1
In soluble nickel salt is Ni (NO in the step (1)3)2·6H2O, soluble cobaltatess are Co (NO3)2·6H2O。
3. the preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor, its feature exist according to claim 1
In citric acid in the step (3)：Sodium chloride or sodium sulphate are 1 in molar ratio：25.
4. the preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor, its feature exist according to claim 1
In protection gas is H in the step (3)2、N2, one or more combination in Ar.
5. the preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor, its feature exist according to claim 1
In step (5) electrolyte is aqueous electrolyte, and concentration is (2~6) mol/L.
6. the preparation method of cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor, its feature exist according to claim 5
In the electrolyte is KOH solution.
7. cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor that the preparation method as described in claim any one of 1-6 obtains.
8. cobalt acid nickel/three-dimensional porous carbon Asymmetric Supercapacitor according to claim 7, it is characterised in that the positive pole
Material is sea urchin shape, and negative material is three-dimensional porous carbon.
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| CN114512349A (en) * | 2022-03-04 | 2022-05-17 | 广东工业大学 | Lignin carbon-transition metal oxide asymmetric supercapacitor and preparation and application thereof |
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| CN109637837A (en) * | 2018-12-14 | 2019-04-16 | 深圳先进技术研究院 | Metal material is used as zinc ion aqueous super capacitor cathode and zinc ion water system hybrid super capacitor |
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| CN111960477A (en) * | 2020-08-20 | 2020-11-20 | 辽宁科技大学 | Preparation method of all-solid-state supercapacitor electrode material |
| CN114512349A (en) * | 2022-03-04 | 2022-05-17 | 广东工业大学 | Lignin carbon-transition metal oxide asymmetric supercapacitor and preparation and application thereof |
| CN114512349B (en) * | 2022-03-04 | 2023-10-27 | 广东工业大学 | Lignin carbon-transition metal oxide asymmetric supercapacitor and preparation and application thereof |
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