CN110047658A - Carbon, electrode material of sulphur codope and preparation method thereof - Google Patents
Carbon, electrode material of sulphur codope and preparation method thereof Download PDFInfo
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- CN110047658A CN110047658A CN201910197880.9A CN201910197880A CN110047658A CN 110047658 A CN110047658 A CN 110047658A CN 201910197880 A CN201910197880 A CN 201910197880A CN 110047658 A CN110047658 A CN 110047658A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- 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
Abstract
The present invention provides a kind of carbon, sulphur codope nickel cobalt double-hydroxide electrode material and preparation method and supercapacitors prepared therefrom.The electrode material includes the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.Preparation method is that nickel salt and cobalt salt are deposited in conductive substrates by constant pressure cathodic electrochemical deposition method；Electrode material and conductive substrates are directly connected to, and do not have to addition bonding agent, therefore effectively reduce resistance, are obtained high performance codope nickel cobalt double-hydroxide electrode material, are overcome the disadvantage of traditional double-hydroxide electrode material high rate performance difference.Preparation method preparation process of the invention is simple, at low cost, the period is short, is suitble to commercial applications.It is anode with this electrode material, active carbon is that the supercapacitor charge-discharge performance of cathode preparation is good, has high power density and energy density；Meet development trend both with supercapacitor high-energy density and high power density.
Description
Technical field
The present invention relates to electrode material for super capacitor, in particular to a kind of carbon, sulphur codope nickel cobalt double-hydroxide
Electrode material and preparation method thereof and the supercapacitor made by it.
Background technique
Supercapacitor is called farad capacitor, gold capacitor, is a kind of new electric energy energy storage component；Supercapacitor
It is generally divided into double electric layers supercapacitor and fake capacitance supercapacitor.Supercapacitor is a kind of in offer high-energy density
It can provide super high power simultaneously, have both the new component of capacitor and battery behavior.Its long service life, environment-adapting ability be strong,
High charge-discharge efficiencies, high-energy density, this is four big distinguishing features of supercapacitor；Therefore the heat studied at present is made it
One of point project.Supercapacitor is made of electrode, electrolyte and diaphragm, and the structure and performance of electrode material are to supercapacitor
Performance play conclusive influence.Transition metal oxide, hydroxide as fake capacitance electrode material for super capacitor,
In the members such as contained metal Ru, Mn, Zn, Ni, Co be known as different price position, the variation between different valence state can occur in electrochemical process
Realize Faraday pseudo-capacitance reaction.Therefore have using the compound that these metallic elements carry out coordination formation with nonmetalloid
Higher theoretical specific capacity.But due to transition metal oxide, hydroxide poorly conductive, so as to cause difference of magnification and longevity is generated
Order short problem.Therefore, lower internal resistance is developed, the electrode material for super capacitor of high-rate characteristics is necessary.
Summary of the invention
The purpose of the present invention is exactly to solve in existing supercapacitor especially fake capacitance electrode material for super capacitor
Resistance is big, difference of magnification, service life is short, at high cost, preparation process is complicated and is difficult to the problem of being mass produced, and provides a kind of benefit
With carbon, the novel nickel cobalt double-hydroxide electrode material of sulphur codope and preparation method thereof: and provide a kind of double by carbon, sulphur
The supercapacitor with high-energy density and high power density of the nickel cobalt double-hydroxide electrode material production of doping.
It is of the present invention using carbon, sulphur codope prepare nickel cobalt double-hydroxide electrode material with increase reactivity and
Reaction site makes electrode material have higher stability；And obtain height ratio capacity, high-rate characteristics, it is low-resistance,
The fake capacitance electrode material for super capacitor for the advantages that charge and discharge coulombic efficiency is high and its supercapacitor of production.
For achieving the above object, the present invention is realized using the technical solution being made of following technical measures.
A kind of carbon provided by the invention, sulphur codope nickel cobalt double-hydroxide electrode material preparation method, according to this
Invention, is that nickel salt and cobalt salt are mixed into uniform solution by the molar ratio of design, and thiocarbamide and glucose are added in uniform solution,
Nickel cobalt double-hydroxide electrode material is prepared using constant voltage cathodic electrochemical deposition method, specifically includes following processing step:
(1) raw material preparation
By nickel salt and cobalt salt, its ratio be 10:1~1:1 for nickel salt and cobalt salt by quality ratio；Then by they be dissolved in from
In sub- water, stirring is to being completely dissolved as uniform solution；
(2) sulphur source and carbon source are added
Being added in above-mentioned uniform solution as the thiocarbamide content of sulphur source is 0.1M；Glucose content as carbon source is 0
~10mM；
(3) conductive substrates are handled
Conductive substrates are cut by design size, and carry out ultrasound respectively with hydrochloric acid, acetone, deionized water and alcohol
It cleans up；
(4) constant voltage cathodic electrochemical deposition is used
Using constant voltage cathodic electrochemical deposition method deposition nickel salt and cobalt salt, the perseverance in the conductive substrates cleaned up
Voltage cathode electrochemical deposition voltage is -2V~-0.7V；Sedimentation time is 0~3600 second；Depositing temperature is 0~100 DEG C；I.e.
Obtain electrode material；
(5) the resulting electrode material of deposition is heat-treated
Deposition obtained electrode material is taken out, is flushed three times with deionized water to five times, is then placed in electrode material
It is 2 hours dry in 60 DEG C of baking ovens, then using the annealing heat-treatment under atmospheric condition, obtain the double hydrogen-oxygens of nickel cobalt of carbon, sulphur codope
Compound electrode material.
Further, the conductive substrates are selected from any one of carbon paper, carbon cloth, carbon fiber or nickel foam.
Further, the conductive substrates are cut to rectangle by design size.
Further, the mass ratio of the nickel salt and cobalt salt is 3:1~1:1.
Further, the nickel salt is nickel nitrate or nickel chloride, and the cobalt salt is cobalt nitrate or cobalt chloride.
Further, the constant voltage cathodic electrochemical deposition voltage is -1.5V~-1V；Sedimentation time be 1200~
1800 seconds；Depositing temperature is 20~35 DEG C.
Further, by the electrode material of constant voltage cathodic electrochemical deposition under atmospheric condition annealing heat-treatment, institute
It is argon gas, nitrogen or air with atmosphere.
Further, temperature is made annealing treatment under the atmospheric condition between 50~350 DEG C, the processing time is 1~300
Minute；Heating rate is 1~5 DEG C/min.
Still further, the annealing heat-treatment temperature is 200 DEG C, heat treatment time is 120 minutes.
The electrode material of preparation method preparation according to the present invention is the nickel cobalt double-hydroxide electricity comprising carbon, sulphur codope
Pole material.
The present invention also provides the nickel cobalt double-hydroxide electrode materials of the carbon prepared by the above method, sulphur codope to surpass
Application in grade capacitor preparation.
In above-mentioned application, the positive electrode of the supercapacitor is by above-mentioned carbon, the nickel cobalt double-hydroxide of sulphur codope
Electrode material is made into.
It include two kinds of magnesium-yttrium-transition metals of nickel ion and cobalt ions in electrode material provided by the invention, nickel ion has higher
Electro-chemical activity, nickel ion and cobalt ions are compounded to form bimetallic by cobalt ions electric conductivity with higher and stability
Closing object can effectively improve the conductivity and electro-chemical activity of compound.The incorporation of carbon can be obviously improved the electric conductivity of material
Can, electrode material internal resistance is effectively reduced；And sulphur is lower than oxygen electronegativity, so the incorporation of sulphur can make the knot of tissue of electrode material
Structure is more flexible, so that the faraday's reaction of Rapid reversible occur on the surface of electrode material, and then promotes the electrification of electrode material
Learn performance；The common incorporation of sulphur, carbon both ensure that the high electrochemical performance of electrode material, while resistance can also be effectively reduced, and obtain
To the electrode material of function admirable.In addition, controlling the glucose content of addition in the range, electrode material can be made to be promoted
Its electric conductivity, while being unlikely to influence the promotion of the specific capacity of electrode material, therefore can utmostly realize that electrode material is each
Item Performance optimization.
The nickel cobalt double-hydroxide electrode material of function admirable prepared by the present invention is applied in supercapacitor, thus
Improve the energy density and power density of supercapacitor.At the same time, for noble ruthenium, nickel salt, cobalt salt former material
Material be easy to get, low in raw material price；It is simple using the method preparation process of electrochemical deposition, and preparation process can be controlled accurately
System；Suitable for large-scale batch production, to realize commercialized possibility.To sum up, provided by the invention this super
Capacitor electrode material and preparation method thereof either still all has in cost and in terms of commercially producing in aspect of performance
Biggish advantage.
The present invention has the advantage that and beneficial technical effect is as follows:
It is of the present invention using carbon, sulphur codope prepare nickel cobalt double-hydroxide electrode material with increase reactivity and
Reaction site makes electrode material have higher stability；And obtain height ratio capacity, high-rate characteristics, it is low-resistance,
The fake capacitance electrode material for super capacitor for the advantages that charge and discharge coulombic efficiency is high；Electrode material prepared by the present invention solves existing
Having supercapacitor, especially the internal resistance of fake capacitance electrode material for super capacitor is big, service life is short, at high cost, preparation process is multiple
It is miscellaneous and be difficult to the problem of being mass produced；The present invention is deposited in conductive substrates by constant voltage cathodic electrochemical deposition method；
Electrode material and conductive substrates are connected directly, and do not have to addition bonding agent, therefore effectively reduce resistance, obtain high performance codope
Nickel cobalt double-hydroxide electrode material overcomes the disadvantage of traditional double-hydroxide electrode material high rate performance difference；And it prepared
Journey is simple, at low cost, the period is short, is suitble to commercial applications.It is anode with this electrode material, active carbon is the super of cathode preparation
Capacitor charging/discharging performance is good, has high power density and energy density；Meet supercapacitor high-energy density and high power
Development trend both with density.
Detailed description of the invention
Fig. 1 is the ac impedance measurement result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 1；
Fig. 2 is the multiplying power property test result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 1；
Fig. 3 is the ac impedance measurement result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 2；
Fig. 4 is the multiplying power property test result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 2；
Fig. 5 is the ac impedance measurement result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 3；
Fig. 6 is the multiplying power property test result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 3；
Fig. 7 is the ac impedance measurement result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 4；
Fig. 8 is the multiplying power property test result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 4；
Fig. 9 is the ac impedance measurement result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 5；
Figure 10 is the multiplying power property test result of nickel cobalt double-hydroxide electrode material prepared by the embodiment of the present invention 5；
Figure 11 is that the supercapacitor of nickel cobalt double-hydroxide electrode material production prepared by the embodiment of the present invention 5 recycles volt
Pacify test result；
Figure 12 is that the super capacitor energy of nickel cobalt double-hydroxide electrode material production prepared by the embodiment of the present invention 5 is close
Degree and saturation effect figure.
Specific embodiment
The technical solution to various embodiments of the present invention is subjected to clear, complete description below, it is clear that described embodiment
Only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's obtained all other embodiment without making creative work belongs to the present invention and is protected
Range.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Following embodiment is raw materials used to be purchased from Chengdu Chang Zhenghua glass Co., Ltd.
Embodiment 1
0.1127g nickel nitrate, 0.0371g cobalt nitrate are weighed, it is equal for stirring in addition 50ml deionized water to being completely dissolved
One solution；Weigh 0.3825g thiocarbamide, 0.0198g glucose is added in above-mentioned solution and stirs to being completely dissolved as uniform solution；
Carbon cloth is cut to the rectangle of 1cm × 1.5cm, distinguishes each ultrasonic cleaning with hydrochloric acid, acetone, deionized water and alcohol
10min。
Using constant voltage cathodic electrochemical deposition, the carbon cloth cleaned up cut is made into conductive substrates, deposition electricity
Pressure -1.5V is reference electrode using Ag/AgCl, and Pt electrode is to electrode, and depositing temperature is 20 DEG C, sedimentation time 1200 seconds；?
To carbon, the nickel cobalt double-hydroxide electrode material of sulphur codope.
The nickel cobalt double-hydroxide electrode material that deposition obtains is taken out, is rinsed three to five times with deionized water, it then will be electric
Pole material is placed in 60 DEG C of baking ovens dry 2 hours, using annealing heat-treatment under the conditions of argon atmosphere, 200 DEG C for the treatment of temperature,
1 DEG C/min of heating rate handles the time 120 minutes, obtains the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The electrode material of preparation is placed in 2M KOH electrolyte, is reference electrode with Ag/AgCl, Pt electrode is to electrode
Electro-chemical test is carried out, test result is 0.5Ag in current density-1When, specific capacity reaches 1255F g-1；Such as Fig. 1 and Fig. 2.
Embodiment 2
0.1127g nickel nitrate, 0.0371g cobalt nitrate are weighed, it is equal for stirring in addition 50ml deionized water to being completely dissolved
One solution；Weigh 0.3825g thiocarbamide, 0.0991g glucose is added in above-mentioned solution and stirs to being completely dissolved as uniform solution；
Nickel foam is cut to the rectangle of 2cm × 1cm, distinguishes each ultrasonic cleaning 10min with hydrochloric acid, acetone, deionized water and alcohol.
Using constant voltage cathodic electrochemical deposition, the nickel foam cleaned up cut is made into conductive substrates, is deposited
Voltage -1.5V, is reference electrode using Ag/AgCl, and Pt electrode is 35 DEG C of depositing temperature, sedimentation time 1800 seconds to electrode；?
To carbon, the nickel cobalt double-hydroxide electrode material of sulphur codope.
The nickel cobalt double-hydroxide electrode material that deposition obtains is taken out, is rinsed three to five times with deionized water, it then will be electric
Pole material is placed in 60 DEG C of baking ovens dry 2 hours, using annealing heat-treatment under the conditions of nitrogen atmosphere, 150 DEG C for the treatment of temperature,
2 DEG C/min of heating rate handles the time 150 minutes, obtains the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The electrode obtained material is placed in 2M KOH electrolyte, is reference electrode with Ag/AgCl, Pt electrode be to electrode into
Row electro-chemical test, test result are 0.5A g in current density-1When, specific capacity reaches 1245F g-1；Such as Fig. 3 and Fig. 4.
Embodiment 3
0.0905g nickel chloride, 0.0301g cobalt chloride are weighed, it is equal for stirring in addition 50ml deionized water to being completely dissolved
One solution；Weigh 0.3825g thiocarbamide, 0.0049g glucose is added in above-mentioned solution and stirs to being completely dissolved as uniform solution；
Carbon paper is cut to the rectangle of 2cm × 1cm, distinguishes each ultrasonic cleaning 10min with hydrochloric acid, acetone, deionized water, alcohol.
Using constant voltage cathodic electrochemical deposition, the carbon paper cleaned up cut is made into conductive substrates, deposition electricity
Pressure -1V, is reference electrode using Ag/AgCl, and Pt electrode is 50 DEG C of depositing temperature, sedimentation time 1800 seconds, to obtain to electrode
Carbon, sulphur codope nickel cobalt double-hydroxide electrode material.
The nickel cobalt double-hydroxide electrode material that deposition obtains is taken out, is rinsed three to five times with deionized water；It then will be electric
Pole material is placed in 60 DEG C of baking ovens dry 2 hours, using annealing heat-treatment under the conditions of air atmosphere, 200 DEG C for the treatment of temperature
Heat treatment 120 minutes, wherein heating rate is 3 DEG C/min, obtains the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The electrode obtained material is placed in 2M KOH electrolyte, is reference electrode with Ag/AgCl, Pt electrode be to electrode into
Row electro-chemical test, test result are 1A g in current density-1When, specific capacity reaches 2177F g-1, when current density increases by 50
Times when, still have 69.7% conservation rate；Such as Fig. 5 and Fig. 6.
Embodiment 4
0.0905g nickel chloride, 0.0301g cobalt chloride are weighed, it is equal for stirring in addition 50ml deionized water to being completely dissolved
One solution；Weigh 0.3825g thiocarbamide, 0.0065g glucose is added in above-mentioned solution and stirs to being completely dissolved as uniform solution；
Carbon fiber is cut to the rectangle of 2cm × 1cm, distinguishes each ultrasonic cleaning 10min with hydrochloric acid, acetone, deionized water, alcohol.
Using constant voltage cathodic electrochemical deposition, the carbon fiber cleaned up cut is made into conductive substrates, is deposited
Voltage -2V is reference electrode using Ag/AgCl, and Pt electrode is to electrode, and sedimentation time 1800 seconds, depositing temperature was 100 DEG C,
Obtain the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The nickel cobalt double-hydroxide electrode material that deposition obtains is taken out, is rinsed three to five times with deionized water；It then will be electric
Pole is placed in 60 DEG C of baking ovens dry 2 hours, using 350 DEG C under the conditions of argon atmosphere, is heat-treated 0 minute, wherein heating speed
Rate is 4 DEG C/min, obtains the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The electrode obtained material is placed in 2M KOH electrolyte, is reference electrode with Ag/AgCl, Pt electrode be to electrode into
Row electro-chemical test, test result are 1A g in current density-1When, specific capacity reaches 2106F g-1, when current density increases by 50
Times when, have 58% conservation rate；Such as Fig. 7 and Fig. 8.
Embodiment 5
0.0905g nickel chloride, 0.0301g cobalt chloride are weighed, it is equal for stirring in addition 50ml deionized water to being completely dissolved
One solution；Weigh 0.3825g thiocarbamide, 0.0049g glucose is added in above-mentioned solution and stirs to being completely dissolved as uniform solution；
Nickel foam is cut to the rectangle of 2cm × 1cm, distinguishes each ultrasonic cleaning 10min with hydrochloric acid, acetone, deionized water, alcohol.
Using constant voltage cathodic electrochemical deposition, the nickel foam cleaned up cut is made into conductive substrates, is deposited
Voltage -0.7V, is reference electrode using Ag/AgCl, and Pt electrode is to steep sedimentation time 3600 seconds, depositing temperature 0 to electrode
DEG C, obtain the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The nickel cobalt double-hydroxide electrode material that deposition obtains is taken out, is rinsed three to five times with deionized water；It then will be electric
Pole material is placed in 60 DEG C of baking ovens dry 2 hours, is heat-treated using under the conditions of nitrogen atmosphere, 50 DEG C for the treatment of temperature, handles
Time 300 minutes；Obtain the nickel cobalt double-hydroxide electrode material of carbon, sulphur codope.
The electrode obtained material is placed in 2M KOH electrolyte, is reference electrode with Ag/AgCl, Pt electrode be to electrode into
Row electro-chemical test, test result are 0.5A g in current density-1When, specific capacity reaches 2083.3F g-1, when current density increases
When adding 100 times, there is 69.9% conservation rate；Such as Fig. 9 and Figure 10.
In addition, the nickel cobalt double-hydroxide electrode material of the carbon that the present invention also provides a kind of by above-mentioned preparation, sulphur codope
Expect the application in supercapacitor preparation.
The supercapacitor, including positive and negative electrode, wherein positive electrode is by the electrode material for preparing in above-described embodiment 5
It is fabricated to.Specific production method: using the electrode material prepared in examples detailed above 5 as positive electrode, commercial activated carbons are negative electrode,
The diaphragm used is polyimide diaphragm；Then positive and negative anodes are faced each other, is separated the two poles of the earth with diaphragm, 6M KOH electrolysis is added
Conductive steel disc, gasket is added in liquid, and application certain pressure, which is sealed in supercapacitor battery shell, to be made.Thus electrode
The prepared supercapacitor of material has high energy density, in 0.2A g-1When, energy density reaches 64Wh Kg-1；
At the same time, also there is high power density, be 14.5Kw Kg in power density-1When；It can reach energy density 20.6Wh Kg-1.As is illustrated by figs. 11 and 12.
Table 1 is in current density 0.5A g-1With 1A g-1When electrode material for super capacitor specific capacity test result and part
Performance indicator
Note: the measurement voltage of specific capacitance is 0-0.45V, and electrolyte is the KOH solution of 2mol/L.
In electrode material provided by the invention include two kinds of magnesium-yttrium-transition metals, nickel ion electro-chemical activity with higher,
Cobalt ions electric conductivity with higher and stability, nickel and cobalt, which are formed compound, can effectively improve nickel cobalt bimetallic compound
Conductivity and electro-chemical activity.
In above-mentioned electrode material provided by the present invention, the incorporation of element sulphur can make materials microstructure structure more flexible,
To which the faraday's reaction of Rapid reversible occur on the surface of material, the chemical property of material is promoted.And the incorporation of carbon
It can be obviously improved the electric conductivity of material, reduce the internal resistance of electrode material.
From above data as can be seen that the above embodiments of the present invention realized the following chievements: using this hair
Supercapacitor electrical property with higher prepared by electrode material provided by bright, especially compared to not mixing any member
For element, the incorporation of element sulphur can be obviously improved the chemical property of electrode material, the especially promotion of specific capacity；And carbon is first
The incorporation of element can be obviously improved the electric conductivity of material；It is mixed while two kinds of carbon, sulphur elements, realizes chemical property
It maximizes, high specific capacity can be obtained, while there are also good electric conductivity and multiplying power properties.
In addition, supercapacitor manufacture craft provided by the invention is simple, low in cost, function admirable, has simultaneously again
Higher energy density and power density have very big market-oriented application potential.
In above-mentioned electrode material provided by the present invention, the foregoing is only a preferred embodiment of the present invention, not
For limiting the present invention, for those skilled in the art, the invention may be variously modified and varied.It is all in the present invention
Spirit and principle within, any modification, equivalent replacement, improvement and so on, should be included in protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of carbon, sulphur codope nickel cobalt double-hydroxide electrode material preparation method, it is characterised in that by nickel salt and cobalt
Salt is mixed into uniform solution by the molar ratio of design, and thiocarbamide and glucose are added in uniform solution, using constant voltage cathode electricity
Chemical deposition prepares nickel cobalt double-hydroxide electrode material, specifically includes following processing step:
(1) raw material preparation
By nickel salt and cobalt salt, its ratio be 10:1~1:1 for nickel salt and cobalt salt by quality ratio；Then they are dissolved in deionized water
In, stirring is to being completely dissolved as uniform solution；
(2) addition of sulphur source and carbon source
Being added in above-mentioned uniform solution as the thiocarbamide content of sulphur source is 0.1M；As carbon source glucose content be 0~
10mM；
(3) conductive substrates are handled
Conductive substrates are cut by design size, and are cleaned by ultrasonic respectively with hydrochloric acid, acetone, deionized water and alcohol
Completely；
(4) constant voltage cathodic electrochemical deposition is used
Using constant voltage cathodic electrochemical deposition method deposition nickel salt and cobalt salt, the constant voltage in the conductive substrates cleaned up
Cathodic electrochemical deposition voltage is -2V~-0.7V；Sedimentation time is 0~3600 second；Depositing temperature is 0~100 DEG C；Obtain
Electrode material；
(5) the resulting electrode material of deposition is heat-treated
Deposition obtained electrode material is taken out, is flushed three times with deionized water to five times, electrode material is then placed in 60 DEG C
It is 2 hours dry in baking oven, then using the annealing heat-treatment under atmospheric condition, obtain the nickel cobalt double-hydroxide of carbon, sulphur codope
Electrode material.
2. preparation method according to claim 1, it is characterised in that the conductive substrates be selected from carbon paper, carbon cloth, carbon fiber,
Or any one of nickel foam.
3. preparation method according to claim 1 or 2, it is characterised in that the conductive substrates are cut to grow by design size
It is rectangular.
4. preparation method according to claim 1, it is characterised in that the mass ratio of the nickel salt and cobalt salt is 3:1~1:
1。
5. according to claim 1 or 4 preparation methods, it is characterised in that the nickel salt is nickel chloride or nickel nitrate；The cobalt
Salt is cobalt chloride or cobalt nitrate.
6. preparation method according to claim 1, it is characterised in that the constant voltage cathodic electrochemical deposition voltage is -1.5V
~-1V；Sedimentation time is 1200~1800 seconds；Depositing temperature is 20~35 DEG C.
7. preparation method according to claim 1, it is characterised in that the obtained electrode material that will deposit is in atmospheric condition
Lower annealing heat-treatment, atmosphere used are argon gas, nitrogen or air.
8. according to claim 1 or 7 preparation methods, it is characterised in that the annealing heat-treatment temperature under atmospheric condition exists
Between 50~350 DEG C, the processing time is 1~300 minute；Heating rate is 1~5 DEG C/min.
9. preparation method according to claim 8, it is characterised in that the annealing heat-treatment temperature is 200 DEG C, when heat treatment
Between be 120 minutes.
10. the double hydrogen-oxygens of the nickel cobalt of the carbon of the preparation of preparation method described in any one of claims 1 to 9 claim, sulphur codope
Application of the compound electrode material in supercapacitor preparation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113363411A (en) * | 2021-05-31 | 2021-09-07 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN113436900A (en) * | 2021-06-28 | 2021-09-24 | 中南林业科技大学 | Nitrogen-doped carbon-based electrode based on nickel-cobalt double hydroxide, preparation method and super capacitor |
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| CN113363411A (en) * | 2021-05-31 | 2021-09-07 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN113363411B (en) * | 2021-05-31 | 2022-07-15 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN113436900A (en) * | 2021-06-28 | 2021-09-24 | 中南林业科技大学 | Nitrogen-doped carbon-based electrode based on nickel-cobalt double hydroxide, preparation method and super capacitor |
| CN113436900B (en) * | 2021-06-28 | 2022-07-15 | 中南林业科技大学 | Nitrogen-doped carbon-based electrode based on nickel-cobalt double hydroxide, preparation method and super capacitor |
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