CN105914046A - Preparation method for hydroxyl-cobalt-carbonate thin-film super capacitor electrode material - Google Patents
Preparation method for hydroxyl-cobalt-carbonate thin-film super capacitor electrode material Download PDFInfo
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- CN105914046A CN105914046A CN201610232255.XA CN201610232255A CN105914046A CN 105914046 A CN105914046 A CN 105914046A CN 201610232255 A CN201610232255 A CN 201610232255A CN 105914046 A CN105914046 A CN 105914046A
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- 239000010409 thin film Substances 0.000 title claims abstract description 28
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KDPJLLVSZLZTAN-UHFFFAOYSA-K cobalt(3+);carbonate;hydroxide Chemical compound [OH-].[Co+3].[O-]C([O-])=O KDPJLLVSZLZTAN-UHFFFAOYSA-K 0.000 title abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000004070 electrodeposition Methods 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- MCRYNZNMVNTSPG-UHFFFAOYSA-L cobalt(2+);oxido hydrogen carbonate Chemical compound [Co+2].OC(=O)O[O-].OC(=O)O[O-] MCRYNZNMVNTSPG-UHFFFAOYSA-L 0.000 claims description 26
- 239000006260 foam Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000004087 circulation Effects 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- H01G11/84—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
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention, which relates to the technical field of the super capacitor electrode material, particularly discloses a preparation method for a hydroxyl-cobalt-carbonate thin-film super capacitor electrode material. The method at least comprises: cleaning, acid soaking, and ultrasonic cleaning are carried out on foamed nickel and then the processed nickel is dried for subsequent application; and the foamed nickel used as a cathode is placed in a reactor and hydrothermal electro-deposition reaction is carried out on the hydrothermal condition. The solution of hydrothermal electro-deposition reaction includes Co(nO3)26H2O with the concentration larger than 0M and not larger than 0.05M, NH4F with the concentration larger than 0M and not larger than 0.024M, and urea with the concentration larger than 0M and not larger than 0.25M; the temperature for the hydrothermal electro-deposition reaction is 90 to 120 DEG C; and the voltage for the hydrothermal electro-deposition reaction is 0.9 to 1.3V. According to the preparation method provided by the embodiment, a thin hydroxyl-cobalt-carbonate film with the strong binding force can be obtained; and when the film is used as an electrode of a super capacitor, the cycling performance is excellent.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field, particularly relate to a kind of hydroxy carbonate cobalt thin film
The preparation method of electrode material for super capacitor.
Background technology
Ultracapacitor (Supercapacitors) is also electrochemical capacitor (Electrochemical capacitor).
There is the superior performances such as high power density, quick charging and discharging capabilities, long cycle life due to it,
Attract substantial amounts of researcher, and in these researcheres, the emphasis of research has been substantially focused on electrode material
Aspect.
At present, electrode material for super capacitor is broadly divided into three major types, (1) carbon-based material, such electrode material
Energy storage principle is electric double layer energy storage, relies on the mode stored electrons of accumulation of static electricity, has good reversibility, but
Its crystallinity is poor, affects electric conductivity；(2) conducting polymer, the maximum advantage of such electrode material is can be
Work under high voltage, but when direct conducting polymer makees electrode material, there is resistance excessive, and many
After secondary charge and discharge cycles, active substance such as easily comes off at the shortcoming；(3) transistion metal compound, such electrode
Material energy storage principle is mainly fake capacitance, so electrode reaction not only occurs on electrode surface, it is also possible to deeply
Electrode interior, this has a great impact for carrying high specific capacitance.Ruthenium-oxide electrode in electrode of third kind material
Material comes into the application stage, but its cost intensive, big for environment pollution, so not being suitable for extensively
Application.In the last few years, researchers generally seek to cheap transistion metal compound replace costliness oxidation
Ruthenium.
Hydroxy carbonate cobalt, as a kind of transistion metal compound, has capacitance characteristic.Yanhua Li et al. uses
Hydro-thermal method is prepared for the composite of hydroxy carbonate cobalt and Graphene, and it is carried out electrochemical property test, knot
Fruit shows that this electrode material has good supercapacitor properties.When electric current density is 0.2A/g, circulate
2400 times, specific capacity is maintained at 364.5F/g (Y Li, J Li, S Zhang, N Wang, Z Zhou.
Co(CO3)0.5(OH)·0.11H2O/Graphene Composites for Supercapacitors, Int.J.
Electrochem.Sci, 2015,10:8005-8016), its specific capacity is less desirable.Therefore its many works
For presoma, in order to obtain cobalt base oxide further, be used as electrode material for super capacitor.BaoWang
Deng, first synthesize high length-diameter ratio Co (CO3)0.5(OH)·0.11H2O nano wire, using it as presoma,
The Co of porous nano line is obtained after 400 DEG C of calcinings3O4.It, when electric current density is 5A/g, has circulated 2000
Secondary, specific capacity is maintained at 240F/g (Bao Wang, Ting Zhu, Hao Bin Wu, Rong Xu, Jun Song
Chen and Xiong Wen(David)Lou.Porous Co3O4nanowires derived from long
Co(CO3)0.5(OH)·0.11H2O nanowires with improved supercapacitive properties,
Nanoscale,2012,4,2145-2149).As can be seen here, existing document thinks that hydroxy carbonate cobalt is not a kind of
Preferably super capacitor material, capacity is low, cycle performance is poor.
Summary of the invention
For solving the problems such as the capacity of above-mentioned existing hydroxy carbonate cobalt existence is low, cycle performance is poor, the present invention is real
Execute example and provide the preparation method of a kind of hydroxy carbonate cobalt thin film electrode material for super capacitor.
In order to reach foregoing invention purpose, the embodiment of the present invention have employed following technical scheme:
The preparation method of a kind of hydroxy carbonate cobalt thin film electrode material for super capacitor, at least comprises the following steps:
Nickel foam is used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning at least 15 minutes respectively, so
After described nickel foam put into the HCl of 0.005～0.01M soaks at least 2h after, take out ultrasonic cleaning,
Dried for standby；
Using nickel foam as negative electrode, it is placed in reactor, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；
Wherein, the solution of described hydrothermal electrodeposition includes that concentration is more than 0M and no more than 0.05M
Co(NO3)2.6H2O, concentration are more than 0M and the NH of no more than 0.024M4F and concentration are more than 0M and not
Carbamide more than 0.25M；The temperature of described hydrothermal electrodeposition reaction is 90～120 DEG C；Described hydrothermal electrodeposition
The voltage of reaction is 0.9～1.3V, and the time of described hydrothermal electrodeposition reaction is 1～3h.
The preparation method of the hydroxy carbonate cobalt thin film electrode material for super capacitor that the above embodiment of the present invention provides,
Because in thermal and hydric environment and there is the condition of High Temperature High Pressure, generate the hydroxy carbonate cobalt being deposited on nickel foam surface
Thin film, it is thus achieved that hydroxy carbonate cobalt thin film bond strength high.The nickel foam of hydroxy carbonate cobalt thin film will be deposited
Make ultracapacitor, be 8mA/cm in electric current density2Time, capacitor reaches 4.2F/cm than electric capacity2, circulation
When about 15000, electric current density is switched to 30mA/cm2, it is the most up to 2.8F/cm than electric capacity2,
When circulation adds up to reach 38000 times, it is still 50% than capacity retention, shows the cycle performance of excellence.
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, below will be to required in embodiment
The accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only the one of the present invention
A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, also
Other accompanying drawing can be obtained according to these accompanying drawings.
Fig. 1 be the embodiment of the present invention prepare hydroxy carbonate cobalt thin film electrode of super capacitor under different conditions
XRD figure；
Fig. 2 is the SEM figure of the hydroxy carbonate cobalt thin film electrode of super capacitor that the embodiment of the present invention prepares；
Fig. 3 is the hydroxy carbonate cobalt thin film electrode of super capacitor TEM figure that the embodiment of the present invention prepares；
Fig. 4 is that the hydroxy carbonate cobalt thin film electrode of super capacitor that the embodiment of the present invention prepares is fast at different scanning
Cyclic voltammetry curve under Du.
Fig. 5 is that the hydroxy carbonate cobalt thin film electrode of super capacitor that the embodiment of the present invention prepares is close at different electric currents
Constant current charge-discharge curve under Du；
Fig. 6 is the life test figure of the hydroxy carbonate cobalt thin film electrode of super capacitor that the embodiment of the present invention prepares.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and reality
Execute example, the present invention is further elaborated.Only should be appreciated that specific embodiment described herein
Only in order to explain the present invention, it is not intended to limit the present invention.
The embodiment of the present invention provides the preparation method of a kind of hydroxy carbonate cobalt thin film electrode material for super capacitor,
At least comprise the following steps:
Nickel foam is used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning at least 15 minutes respectively, so
After described nickel foam put into the HCl of 0.005～0.01M soaks at least 2h after, take out ultrasonic cleaning,
Dried for standby；
Using nickel foam as negative electrode, it is placed in reactor, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；
Wherein, the solution of described hydrothermal electrodeposition includes that concentration is more than 0M and no more than 0.05M
Co(NO3)2.6H2O, concentration are more than 0M and the NH of no more than 0.024M4F and concentration are more than 0M and not
Carbamide more than 0.25M；The temperature of described hydrothermal electrodeposition reaction is 90～120 DEG C；Described hydrothermal electrodeposition
The voltage of reaction is 0.9～1.3V, and the response time of hydrothermal electrodeposition reaction is 1～3h.
In any one embodiment, first nickel foam is carried out, primarily to prevent nickel foam surface
Impurity may cause capacitive property to be deteriorated on preparing material to produce impact.
In a preferred embodiment, when the voltage of hydrothermal electrodeposition reaction is 1.2V, the hydroxy carbonate obtained
Cobalt thin film is under 40kHz supersound process, without film separation, illustrates that the hydroxy carbonate cobalt obtained under this voltage is thin
Film bond strength is good.
In any embodiment, when carrying out hydrothermal electrodeposition reaction, with lamellar cobalt, cystose cobalt or cobalt
Any one in nickel alloy is anode, and these samples, as anode, can go out nickel cobalt ion by anodic solution,
The cobalt ion constantly separated out in make-up solution.
The preparation method of the hydroxy carbonate cobalt thin film electrode material for super capacitor that the embodiment of the present invention provides,
In the thermal and hydric environment of 90～130 DEG C and keep High Temperature High Pressure, generate the hydroxy carbonate being deposited on nickel foam surface
Cobalt thin film, it is thus achieved that hydroxy carbonate cobalt thin film through sonic oscillation, find no thin film and drop phenomenon, and foam
Nickel weightening finish, up to 6mg, reflects that the bond strength of the hydroxy carbonate cobalt thin film of acquisition is high.It is made into super electricity
Container, when testing, is 8mA/cm in electric current density2, reach 4.2F/cm than electric capacity2, circulate 15000
During left and right, electric current density is switched to 30mA/cm2, it is the most up to 2.8F/cm than electric capacity2, circulation is tired
When meter reaches 38000 times, it is still 50% than capacity retention.Understand from these data, this electrode material table
Reveal the cycle performance of excellence.
In order to preferably embody the hydroxy carbonate cobalt thin film electrode material for super capacitor that the embodiment of the present invention provides
Preparation method, further illustrate below by multiple embodiments.
Embodiment 1
(1) by nickel foam successively with acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15min respectively；
(2) nickel foam that then (1) obtains is placed in the HCl of 0.008M immersion 2h, takes out, ultrasonic with pure water
Clean, be dried, stand-by；
(3) nickel foam (2) obtained is respectively as negative electrode, anode, is placed in reactor, and in reactor
That pours into includes 0.05MCo (NO3)2.6H2O、0.005MNH4The reaction solution of F and 0.020M carbamide；
(4) temperature arranging hydrothermal electrodeposition reaction is 100 DEG C, and voltage is 0.9V, hydrothermal electrodeposition reaction 2.0h；
(5) electrode (4) obtained takes out, and cleans with distilled water, dries；
(6) electrode (5) obtained carries out electrochemical property test to it in three electrode test systems.Specifically
The electrode obtained using (5) is as Electrode, and platinum electrode is that bag and calomel electrode are reference electrode to electrode,
When electric current density is 30mA/cm2Time, the ratio electric capacity recording Electrode is 1.5F/cm2。
Embodiment 2
(1) by nickel foam successively with acetone, dehydrated alcohol, deionized water ultrasonic cleaning 150min respectively；
(2) nickel foam that then (1) obtains is placed in the HCl of 0.01M immersion 2h, takes out, ultrasonic with pure water
Clean, be dried, stand-by；
(3) nickel foam (2) obtained is respectively as negative electrode, anode, is placed in reactor, and in reactor
That pours into includes 0.04MCo (NO3)2.6H2O、0.024MNH4The reaction solution of F and 0.25M carbamide；
(4) temperature arranging hydrothermal electrodeposition reaction is 120 DEG C, and voltage is 1.0V, hydrothermal electrodeposition reaction 2.0h；
(5) electrode (4) obtained takes out, and cleans with distilled water, dries；
(6) electrode (5) obtained carries out electrochemical property test to it in three electrode test systems.Specifically
The electrode obtained using (5) is as Electrode, and platinum electrode is that bag and calomel electrode are reference electrode to electrode,
When electric current density is 8mA/cm2Time, the ratio electric capacity recording Electrode is 4.2F/cm2, circulate 15000 times
Left and right, increases to 30mA/cm by electric current density2Time, the ratio electric capacity recording Electrode is 2.8F/cm2,
When circulative accumulation reaches 53000 times, it is 50% than capacity retention.
The electrode sample simultaneously obtained this embodiment carries out XRD test under different conditions, SEM schemes to see
Examine under the cyclic voltammetry curve under analysis, TEM figure observation analysis, different scanning speed, different electric current density
Constant current charge-discharge curve and cycle life curve.
From fig. 1, it can be seen that after a cyclic voltammetry, hydroxy carbonate cobalt electrode thin film is turned by cobalt carbonate
Change Co into2O3, divalent cobalt ion is changed for trivalent cobalt ion；Carry out again through repeatedly constant current charge-discharge
During test, find that electrode substance becomes CoOOH；Electrode after 53000 circulations is surveyed again
Examination, obtaining electrode composition is CoOOH.
As can be seen from Figure 2 in hydrothermal electrodeposition course of reaction, nickel foam framing structure grows one
The dense uniform thin film that layer is the thickest；Amplify it appeared that their pattern is in the hairbrush shape stood upside down, this pattern
It is advantageous to the infiltration of electrolyte solution, the transport pathway shortening ion is had great significance.
Embodiment 3
(1) by nickel foam successively with acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15min respectively；
(2) nickel foam that then (1) obtains is placed in the HCl of 0.005M immersion 2h, takes out, ultrasonic with pure water
Clean, be dried, stand-by；
(3) nickel foam (2) obtained is respectively as negative electrode, anode, is placed in reactor, and in reactor
That pours into includes 0.02MCo (NO3)2.6H2O、0.01MNH4The reaction solution of F and 0.1M carbamide；
(4) temperature arranging hydrothermal electrodeposition reaction is 130 DEG C, and voltage is 1.2V, hydrothermal electrodeposition reaction 2.0h；
(5) electrode (4) obtained takes out, and cleans with distilled water, dries；
(6) electrode (5) obtained carries out electrochemical property test to it in three electrode test systems.Specifically
The electrode obtained using (5) is as Electrode, and platinum electrode is that bag and calomel electrode are reference electrode to electrode,
When electric current density is 30mA/cm2Time, the ratio electric capacity recording Electrode is 1.8F/cm2。
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent or the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (2)
1. a preparation method for hydroxy carbonate cobalt thin film electrode material for super capacitor, at least includes following step
Rapid:
Nickel foam is used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning at least 15 minutes respectively, so
After described nickel foam put into the HCl of 0.005～0.01M soaks at least 2h after, take out ultrasonic cleaning,
Dried for standby；
Using nickel foam as negative electrode, it is placed in reactor, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；
Wherein, the solution of described hydrothermal electrodeposition includes that concentration is more than 0M and no more than 0.05M
Co(NO3)2.6H2O, concentration are more than 0M and the NH of no more than 0.024M4F and concentration are more than 0M and not
Carbamide more than 0.25M；The temperature of described hydrothermal electrodeposition reaction is 90～120 DEG C；Described hydrothermal electrodeposition
The voltage of reaction is 0.9～1.3V, and the time of described hydrothermal electrodeposition reaction is 1～3h.
2. preparation method as claimed in claim 1, it is characterised in that: also include with lamellar cobalt, cystose
Any one in cobalt or cobalt-nickel alloy is anode.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610232255.XA CN105914046B (en) | 2016-04-14 | 2016-04-14 | The preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor |
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|---|---|---|---|
| CN201610232255.XA CN105914046B (en) | 2016-04-14 | 2016-04-14 | The preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor |
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| Publication Number | Publication Date |
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| CN105914046A true CN105914046A (en) | 2016-08-31 |
| CN105914046B CN105914046B (en) | 2018-07-27 |
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| CN201610232255.XA Expired - Fee Related CN105914046B (en) | 2016-04-14 | 2016-04-14 | The preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor |
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Cited By (3)
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| CN108735517A (en) * | 2018-05-30 | 2018-11-02 | 大连交通大学 | A kind of basic zinc carbonate electrode material for super capacitor and preparation method thereof |
| CN109837559A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of FeOOH-nickel-ferric spinel integrated electrode preparation method of hydro-thermal auxiliary |
| CN109880292A (en) * | 2019-01-22 | 2019-06-14 | 中国海洋大学 | The preparation method of polymer matrix high-dielectric composite material based on core-shell structure three-dimensional framework |
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| CN101525752A (en) * | 2009-04-21 | 2009-09-09 | 湖南大学 | Clean production method for high-purity cobaltosic oxide powder |
| CN103543184A (en) * | 2013-10-18 | 2014-01-29 | 浙江大学 | Gas-sensitive sensor based on cobaltosic oxide nanoneedle as well as preparation method thereof |
| CN104609479A (en) * | 2015-02-11 | 2015-05-13 | 天津理工大学 | Method for preparing Co3O4 nanoribbon |
| CN104681299A (en) * | 2015-03-27 | 2015-06-03 | 吉林化工学院 | Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof |
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| CN101525752A (en) * | 2009-04-21 | 2009-09-09 | 湖南大学 | Clean production method for high-purity cobaltosic oxide powder |
| CN103543184A (en) * | 2013-10-18 | 2014-01-29 | 浙江大学 | Gas-sensitive sensor based on cobaltosic oxide nanoneedle as well as preparation method thereof |
| CN104609479A (en) * | 2015-02-11 | 2015-05-13 | 天津理工大学 | Method for preparing Co3O4 nanoribbon |
| CN104681299A (en) * | 2015-03-27 | 2015-06-03 | 吉林化工学院 | Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109837559A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of FeOOH-nickel-ferric spinel integrated electrode preparation method of hydro-thermal auxiliary |
| CN109837559B (en) * | 2017-11-28 | 2021-08-06 | 中国科学院大连化学物理研究所 | Hydrothermal-assisted preparation method of hydroxyl iron oxide-nickel iron hydrotalcite integrated electrode |
| CN108735517A (en) * | 2018-05-30 | 2018-11-02 | 大连交通大学 | A kind of basic zinc carbonate electrode material for super capacitor and preparation method thereof |
| CN109880292A (en) * | 2019-01-22 | 2019-06-14 | 中国海洋大学 | The preparation method of polymer matrix high-dielectric composite material based on core-shell structure three-dimensional framework |
| CN109880292B (en) * | 2019-01-22 | 2020-03-06 | 中国海洋大学 | Preparation method of polymer-based high-dielectric composite material based on three-dimensional skeleton with core-shell structure |
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