CN105914046B - The preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor - Google Patents
The preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor Download PDFInfo
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- CN105914046B CN105914046B CN201610232255.XA CN201610232255A CN105914046B CN 105914046 B CN105914046 B CN 105914046B CN 201610232255 A CN201610232255 A CN 201610232255A CN 105914046 B CN105914046 B CN 105914046B
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- thin film
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to electrode material for super capacitor technical fields, specifically disclose a kind of preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor.The method at least includes the following steps：Nickel foam is cleaned, acid soak and is cleaned by ultrasonic, dried for standby；It using nickel foam as cathode, is placed in reaction kettle, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；Wherein, the solution of the hydrothermal electrodeposition includes that concentration is more than 0M and the Co (NO no more than 0.05M3)2.6H2O, concentration is more than 0M and the NH no more than 0.024M4F and concentration are more than 0M and the urea no more than 0.25M；The temperature of the hydrothermal electrodeposition reaction is 90~120 DEG C；The voltage of the hydrothermal electrodeposition reaction is 0.9~1.3V.The above embodiment of the present invention provide hydroxy carbonate cobalt thin film electrode material for super capacitor preparation method, the strong hydroxy carbonate cobalt thin film of binding force can be obtained, as ultracapacitor electrode when, show excellent cycle characteristics.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field more particularly to a kind of super electricity of hydroxy carbonate cobalt thin film
The preparation method of container electrode material.
Background technology
Ultracapacitor (Supercapacitors) be also electrochemical capacitor (Electrochemical
capacitor).Since it is with high power density, quick charging and discharging capabilities, the superior performance such as long cycle life,
Attract a large amount of researcher, and in these researchers, the emphasis of research is substantially focused on electrode material aspect.
Currently, electrode material for super capacitor is broadly divided into three categories, and (1) carbon-based material, such electrode material energy storage original
Reason is electric double layer energy storage, by the mode stored electrons of accumulation of static electricity, has good invertibity, but its crystallinity is poor, influences to lead
Electrically；(2) conducting polymer, such electrode material biggest advantage are can to work under high voltages, but directly use conductive
When polymer makees electrode material, it is excessive that there are resistance, and after multiple charge and discharge cycles, and active material, which is easy to fall off, etc. lacks
Point；(3) transistion metal compound, such electrode material energy storage principle is mainly fake capacitance, so electrode reaction not only occurs on
Electrode surface can also go deep into electrode interior, this has a great impact for improving specific capacitance.Oxygen in electrode of third kind material
Change ruthenium electrode material and comes into the application stage, but its is expensive, causes serious pollution to the environment, so not being suitable for answering extensively
With.In recent years, researchers generally seek to cheap transistion metal compound to replace expensive ruthenium-oxide.
Hydroxy carbonate cobalt has capacitance characteristic as a kind of transistion metal compound.Yanhua Li et al. people use hydro-thermal method
It is prepared for the composite material of hydroxy carbonate cobalt and graphene, electrochemical property test is carried out to it, the results showed that this electrode material
Material has good supercapacitor properties.When current density is 0.2A/g, recycle 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), specific capacity is not very
It is ideal.Therefore it is mostly used as electrode material for super capacitor as presoma further to obtain cobalt base oxide.
BaoWang etc. synthesizes high length-diameter ratio Co (CO first3)0.5(OH)·0.11H2O nano wires, using it as presoma, through 400
DEG C calcining after obtain porous nano line Co3O4.It has been recycled 2000 times, specific capacity is maintained at when current density is 5A/g
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).It can be seen that it is a kind of ideal super capacitor material that existing literature, which thinks hydroxy carbonate cobalt not, capacity is low, cyclicity
It can be poor.
Invention content
The problems such as to solve low capacity existing for above-mentioned existing hydroxy carbonate cobalt, poor circulation, the embodiment of the present invention carries
A kind of preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor is supplied.
In order to reach foregoing invention purpose, the embodiment of the present invention uses the following technical solution：
A kind of preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor, at least includes the following steps：
Nickel foam is cleaned by ultrasonic at least 15 minutes with acetone, absolute ethyl alcohol, deionized water respectively successively, it then will be described
Nickel foam is put into impregnate at least 2h in the HCl of 0.005~0.01M after, take out be cleaned by ultrasonic, dried for standby；
It using nickel foam as cathode, is placed in reaction kettle, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；
Wherein, the solution of the hydrothermal electrodeposition includes that concentration is more than 0M and the Co (NO no more than 0.05M3)2.6H2O, dense
NH of the degree more than 0M and no more than 0.024M4F and concentration are more than 0M and the urea no more than 0.25M；The hydrothermal electrodeposition is anti-
The temperature answered is 90~120 DEG C；The voltage of the hydrothermal electrodeposition reaction is 0.9~1.3V, the hydrothermal electrodeposition reaction
Time is 1~3h.
The preparation method for 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 the condition with high temperature and pressure, generation are deposited on the hydroxy carbonate cobalt thin film of foam nickel surface, the hydroxyl of acquisition
Base carbonic acid cobalt thin film bond strength is high.Ultracapacitor is made in the nickel foam that deposited hydroxy carbonate cobalt thin film, it is close in electric current
Degree is 8mA/cm2When, capacitor specific capacitance reaches 4.2F/cm2, when recycling 15000 or so, current density is switched into 30mA/
cm2, it is 2.8F/cm that specific capacitance, which is still up to,2, when cycle is added up up to 38000 times, specific capacitance conservation rate is still 50%, is shown excellent
Different cycle performance.
Description of the drawings
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is XRD of the hydroxy carbonate cobalt thin film electrode of super capacitor under different conditions made from the embodiment of the present invention
Figure；
Fig. 2 is the SEM figures of hydroxy carbonate cobalt thin film electrode of super capacitor made from the embodiment of the present invention；
Fig. 3 is that hydroxy carbonate cobalt thin film electrode of super capacitor TEM made from the embodiment of the present invention schemes；
Fig. 4 is hydroxy carbonate cobalt thin film electrode of super capacitor made from the embodiment of the present invention under different scanning speed
Cyclic voltammetry curve.
Fig. 5 is hydroxy carbonate cobalt thin film electrode of super capacitor made from the embodiment of the present invention under different current densities
Constant current charge-discharge curve；
Fig. 6 is the life test figure of hydroxy carbonate cobalt thin film electrode of super capacitor made from the embodiment of the present invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor, at least wraps
Include following steps：
Nickel foam is cleaned by ultrasonic at least 15 minutes with acetone, absolute ethyl alcohol, deionized water respectively successively, it then will be described
Nickel foam is put into impregnate at least 2h in the HCl of 0.005~0.01M after, take out be cleaned by ultrasonic, dried for standby；
It using nickel foam as cathode, is placed in reaction kettle, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；
Wherein, the solution of the hydrothermal electrodeposition includes that concentration is more than 0M and the Co (NO no more than 0.05M3)2.6H2O, dense
NH of the degree more than 0M and no more than 0.024M4F and concentration are more than 0M and the urea no more than 0.25M；The hydrothermal electrodeposition is anti-
The temperature answered is 90~120 DEG C；The voltage of the hydrothermal electrodeposition reaction is 0.9~1.3V, the reaction of hydrothermal electrodeposition reaction
Time is 1~3h.
In any one embodiment, first nickel foam is cleaned, primarily to preventing nickel foam surface impurity pair
Material is prepared to have an impact and capacitive property may be caused to be deteriorated.
In a preferred embodiment, when the voltage of hydrothermal electrodeposition reaction is 1.2V, obtained hydroxy carbonate cobalt thin film
Under 40kHz supersound process, no film separation illustrates that the hydroxy carbonate cobalt thin film bond strength obtained under the voltage is good.
In any embodiment, when carrying out hydrothermal electrodeposition reaction, in sheet cobalt, foam-like cobalt or cobalt-nickel alloy
It is any be anode, these samples can be gone out nickel cobalt ion by anodic solution, be constantly precipitated in make-up solution as anode
Cobalt ions.
The preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor provided in an embodiment of the present invention, 90~
In 130 DEG C of thermal and hydric environment and high temperature and pressure is kept, generates the hydroxy carbonate cobalt thin film for being deposited on foam nickel surface, acquisition
Hydroxy carbonate cobalt thin film finds no film and falls phenomenon, and nickel foam weightening reflects acquisition up to 6mg through sonic oscillation
The bond strength of hydroxy carbonate cobalt thin film is high.It is made into ultracapacitor, is 8mA/cm in current density when being tested2,
Specific capacitance reaches 4.2F/cm2, when recycling 15000 or so, current density is switched into 30mA/cm2, specific capacitance, which is still up to, is
2.8F/cm2, when cycle is added up up to 38000 times, specific capacitance conservation rate is still 50%.It is found that the electrode material from these data
Show excellent cycle performance.
In order to preferably embody the system of hydroxy carbonate cobalt thin film electrode material for super capacitor provided in an embodiment of the present invention
Preparation Method is further illustrated below by multiple embodiments.
Embodiment 1
(1) nickel foam is cleaned by ultrasonic 15min respectively with acetone, absolute ethyl alcohol, deionized water successively；
(2) nickel foam that then (1) obtains, which is placed in the HCl of 0.008M, impregnates 2h, takes out, is cleaned by ultrasonic with pure water, is done
It is dry, for use；
(3) nickel foam for obtaining (2) is placed in respectively as cathode, anode in reaction kettle, and poured into reaction kettle
Include 0.05MCo (NO3)2.6H2O、0.005MNH4The reaction solution of F and 0.020M urea；
(4) temperature that setting hydrothermal electrodeposition reacts is 100 DEG C, voltage 0.9V, and hydrothermal electrodeposition reacts 2.0h；
(5) electrode for obtaining (4) takes out, wash with distilled water, drying；
(6) electrode that (5) obtain is subjected to electrochemical property test in three electrode test systems to it.Specifically with
(5) electrode obtained is as Electrode, and platinum electrode is to electrode, and packet and calomel electrode are reference electrode, when current density is
30mA/cm2When, the specific capacitance for measuring Electrode is 1.5F/cm2。
Embodiment 2
(1) nickel foam is cleaned by ultrasonic 150min respectively with acetone, absolute ethyl alcohol, deionized water successively；
(2) nickel foam that then (1) obtains, which is placed in the HCl of 0.01M, impregnates 2h, takes out, is cleaned by ultrasonic with pure water, is done
It is dry, for use；
(3) nickel foam for obtaining (2) is placed in respectively as cathode, anode in reaction kettle, and poured into reaction kettle
Include 0.04MCo (NO3)2.6H2O、0.024MNH4The reaction solution of F and 0.25M urea；
(4) temperature that setting hydrothermal electrodeposition reacts is 120 DEG C, voltage 1.0V, and hydrothermal electrodeposition reacts 2.0h；
(5) electrode for obtaining (4) takes out, wash with distilled water, drying；
(6) electrode that (5) obtain is subjected to electrochemical property test in three electrode test systems to it.Specifically with
(5) electrode obtained is as Electrode, and platinum electrode is to electrode, and packet and calomel electrode are reference electrode, when current density is
8mA/cm2When, the specific capacitance for measuring Electrode is 4.2F/cm2, recycle 15000 times or so, current density increased into 30mA/
cm2When, the specific capacitance for measuring Electrode is 2.8F/cm2, when circulative accumulation is up to 53000 times, specific capacitance conservation rate is 50%.
The electrode sample obtained simultaneously to the embodiment carries out XRD tests, SEM figures observation analysis, TEM under different conditions
It cyclic voltammetry curve under figure observation analysis, different scanning speed, the constant current charge-discharge curve under different current densities and follows
Ring life curve.
From fig. 1, it can be seen that after the test of one cycle volt-ampere, hydroxy carbonate cobalt electrode film is converted to by cobalt carbonate
Co2O3, divalent cobalt ion conversion is for trivalent cobalt ions；When being tested again by multiple constant current charge-discharge, electrode substance is found
Become CoOOH；Electrode after 53000 cycles is tested again, and it is CoOOH to obtain electrode composition.
As can be seen from Figure 2 in hydrothermal electrodeposition reaction process, grown in nickel foam skeleton structure one layer very thick
Dense uniform film；It can be found that their pattern is in the hairbrush shape to stand upside down, it is molten that this pattern is advantageous to electrolyte for amplification
The infiltration of liquid, the transport pathway to shortening ion have great significance.
Embodiment 3
(1) nickel foam is cleaned by ultrasonic 15min respectively with acetone, absolute ethyl alcohol, deionized water successively；
(2) nickel foam that then (1) obtains, which is placed in the HCl of 0.005M, impregnates 2h, takes out, is cleaned by ultrasonic with pure water, is done
It is dry, for use；
(3) nickel foam for obtaining (2) is placed in respectively as cathode, anode in reaction kettle, and poured into reaction kettle
Include 0.02MCo (NO3)2.6H2O、0.01MNH4The reaction solution of F and 0.1M urea；
(4) temperature that setting hydrothermal electrodeposition reacts is 130 DEG C, voltage 1.2V, and hydrothermal electrodeposition reacts 2.0h；
(5) electrode for obtaining (4) takes out, wash with distilled water, drying；
(6) electrode that (5) obtain is subjected to electrochemical property test in three electrode test systems to it.Specifically with
(5) electrode obtained is as Electrode, and platinum electrode is to electrode, and packet and calomel electrode are reference electrode, when current density is
30mA/cm2When, the specific capacitance for measuring Electrode is 1.8F/cm2。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (2)
1. a kind of preparation method of hydroxy carbonate cobalt thin film electrode material for super capacitor, at least includes the following steps：
Nickel foam is cleaned by ultrasonic at least 15 minutes with acetone, absolute ethyl alcohol, deionized water respectively successively, then by the foam
Nickel is put into impregnate at least 2h in the HCl of 0.005~0.01M after, take out be cleaned by ultrasonic, dried for standby；
It using nickel foam as cathode, is placed in reaction kettle, carries out hydrothermal electrodeposition reaction under hydrothermal conditions；
Wherein, the solution of the hydrothermal electrodeposition includes that concentration is more than 0M and the Co (NO no more than 0.05M3)2.6H2O, concentration is big
In 0M and no more than the NH of 0.024M4F and concentration are more than 0M and the urea no more than 0.25M；The hydrothermal electrodeposition reaction
Temperature is 90~120 DEG C；The voltage of the hydrothermal electrodeposition reaction is 0.9~1.3V, the time of the hydrothermal electrodeposition reaction
For 1~3h.
2. preparation method as described in claim 1, it is characterised in that：Further include being closed with sheet cobalt, foam-like cobalt or cobalt nickel
Any one of gold is anode.
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| 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 |
| CN108735517B (en) * | 2018-05-30 | 2020-09-25 | 大连交通大学 | Basic zinc carbonate supercapacitor electrode material and preparation method thereof |
| 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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|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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