CN109411244A - A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode - Google Patents
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode Download PDFInfo
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- CN109411244A CN109411244A CN201811186740.3A CN201811186740A CN109411244A CN 109411244 A CN109411244 A CN 109411244A CN 201811186740 A CN201811186740 A CN 201811186740A CN 109411244 A CN109411244 A CN 109411244A
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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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- 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
- H01G11/24—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
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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
- H01G11/46—Metal oxides
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of titanium dioxide/double-metal hydroxide combination electrode preparation methods, comprising the following steps: (1) cleans titanium silk, pass through anodic oxidation after dry and synthesize TiO on titanium silk2NTs；(2) being polarised improves its electric conductivity；(3) deposition liquid needed for preparing electrochemical deposition；(4) to TiO under three-electrode system2NTs is using chronoptentiometry electrochemical deposition and dry after cleaning.The present invention have the good mechanical property of electrode, the latter be it is two-dimensional laminar structured, large specific surface area has good charge storage and ion-diffusibility.Compound acquisition in this way has the lineation electrode of excellent mechanical performances and chemical property simultaneously, and the electrodeposition process sample preparation time is short, high-efficient, laboratory apparatus, it is easy to operate, the sedimentary that electro-deposition is formed is uniform and smooth, it is often more important that the thickness of sedimentary is controllable.
Description
Technical field
The present invention relates to a kind of preparation method of combination electrode, specifically a kind of titanium dioxide/double-metal hydroxide is multiple
The preparation method of composite electrode, belongs to electrochemical field.
Background technique
In recent years, portable intelligent electronic device development is swift and violent, and the development of electronic device is too busy to get away corresponding efficient soft
Property energy storage device, so, using carbon fiber, conductive gold layer category fabric and CNT coating cotton fabric/paper as flexible electrical made of substrate
Container comes into being.But these matrixes involve great expense, competition of market economy ability is weak, it is difficult to which invested in plant metaplasia produces.And Ti
For silk compared with above-mentioned material, it is a kind of basis material of great potential that cost is lower, conduct electricity very well, internal resistance is smaller.
Titanium dioxide is a kind of important functional material, due at low cost, hypotoxicity, more environmental protection and has goodization
Learn stability, attract more and more concerns in recent years, be widely used in photochemical catalyst, pollutant detergent, lithium ion battery,
The environment such as supercapacitor, solar battery and energy field.In the application of supercapacitor, titanium dioxide is frequently as one kind
Common active material of positive electrode.Under current technology, the titanium dioxide obtained by different preparation methods often possesses different
Form, and the titanium dioxide of different shape, the performance on super electrical property are also multifarious.Some researches show that various common
In form (such as: nanotube, nano wire, nanoparticle), there are higher order structures and big ratio by prepared by anodic oxidation
The TiO of surface area2Nano-tube array shows higher charge collection efficiency and light capture rate.But single TiO2 receives
Mitron there are poorly conductive, electro-chemical activity is low the problems such as, which greatly limits its applications in efficient supercapacitor.And
And for the remodeling method of TiO2 nanotube itself, such as: in Ar, NH3Or H2Ambient anneal, electrochemical hydrogenation processing, metal
Ion doping etc., it is extremely limited to the improvement of its capacitor performance.Therefore, by TiO2 nanotube and other transition metal oxides
Or hydroxide progress is compound, becomes a promising research direction.
Summary of the invention
In view of the above-mentioned problems of the prior art, the object of the present invention is to provide a kind of titanium dioxide/bimetallic hydrogen-oxygens
The preparation method of compound combination electrode, to improve the chemical property and electro-chemical activity of electrode, meanwhile, so that electrode material
Pattern is optimised, to improve the preparation efficiency of electrode.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of titanium dioxide/double-metal hydroxide is compound
The preparation method of electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, the electrolyte solution used are 0.4%NH4F, the ethylene glycol of 10%vol deionized water
Solution；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition nickel salt, cobalt salt, ammonium chloride and deionized water is mixed；
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition successively uses deionized water after reaction, and dehydrated alcohol cleans more than three times repeatedly, and
10-12h is dried in vacuum oven under the conditions of 70 DEG C of temperature, obtains TiO later2NTs/Ni-Co LDH combination electrode.
Preferably, the anodic oxidation condition in step (1) is voltage 50-80V, oxidization time 1-2h.
Preferably, the cobalt salt in step (3) is Co (NO3)2·6H2O, nickel salt are Ni (NO3)2·6H2O。
Preferably, the electrolyte in step (3) by 2mmol Co (NO3)2·6H2O, the Ni (NO of 2-6mmol3)2·6H2O
With the NH of 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
Preferably, the condition of the chronoptentiometry electrochemical deposition in step (4) is deposition current 0.01-0.02A, deposition
Duration 900s.
It is compared with existing technology, the present invention provides a kind of linear electrode of super capacitor, including nano titania
Manage (TiO2NTs) and using above-mentioned material as the electro-deposition of substrate double-metal hydroxide is obtained, and the present invention is by TiO2NTs
With double-metal hydroxide by the method for electrochemical deposition carry out it is compound prepare linear electrode of super capacitor, wherein Ti are filled
When the effect of collector, while the good mechanical property of electrode is also assigned, the latter is two-dimensional laminar structured, specific surface area
Greatly, there are good charge storage and ion-diffusibility.Compound acquisition in this way has excellent mechanical performances simultaneously
With the lineation electrode of chemical property, and the electrodeposition process sample preparation time is short, high-efficient, and laboratory apparatus is easy to operate,
The sedimentary that electro-deposition is formed is uniform and smooth, it is often more important that the thickness of sedimentary is controllable.
Detailed description of the invention
Fig. 1 is TiO2The scanning electron microscope (SEM) photograph of NTs/Ni-Co LDH combination electrode, wherein a, b, c, d be successively 50um,
Under the conditions of 5um, 1um, 100um multiple；
Fig. 2 is TiO2Chemical property of the NTs/Ni-Co LDH combination electrode under different anodic oxidation voltages is surveyed
Attempt；
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment 1:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 50V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 2mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.02A deposits duration 900s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 1490.87mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 80%.
Embodiment 2:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 65V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 2mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.02A deposits duration 900s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 1288mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 88%.
Embodiment 3:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 80V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 2mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.02A deposits duration 900s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 981mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 58%.
Embodiment 4:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 65V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 2mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.01A deposits duration 900s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 889mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 88%.
Embodiment 5:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 80V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 2mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.02A deposits duration 1800s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 925mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 55.7%.
Embodiment 6:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 50V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 4mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.02A deposits duration 900s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 1150mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 76%.
Embodiment 7:
A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode, comprising the following steps:
(1) by high-purity titanium silk be cut to average length be 10cm several segments, be sequentially placed into dilute hydrochloric acid solution, go from
Respectively it is cleaned by ultrasonic 10min in sub- water and dehydrated alcohol, is then placed into drying in 70 DEG C of vacuum ovens and passes through sun after 5-9 hours
Pole oxidation synthesizes TiO on titanium silk2NTs, anodic oxidation condition are voltage 50V, oxidization time 1-2h.The electrolyte solution used
For 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition, i.e., by nickel salt Ni (NO3)2·6H2O, cobalt salt Co (NO3)2·
6H2O, ammonium chloride and deionized water are mixed, and electrolyte is by the Co (NO of 2mmol3)2·6H2O, the Ni (NO of 6mmol3)2·
6H2The NH of O and 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is
Working electrode, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses timing
Potentiometry electrochemical deposition, reaction condition are as follows: deposition current 0.02A deposits duration 900s.After reaction, successively using going
Ionized water, dehydrated alcohol clean more than three times repeatedly, and dry 10-12h under the conditions of in a vacuum drying oven in 70 DEG C of temperature,
TiO is obtained later2NTs/Ni-Co LDH combination electrode.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in current density 2mA/
cm2When can reach 1028mF/cm2,；Cycle charge-discharge 2000 encloses, cycle efficieny 70%.
More than Comprehensive Correlation each embodiment, it can be seen that the TiO being prepared2NTs/Ni-Co LDH combination electrode, such as
Shown in Fig. 1, what can be will be apparent that sees TiO2Nanotube (TiO2NTs tubular structure) can be seen by scanning electron microscope
Its microscopic appearance is observed, i.e. tubulose is similar with the combination of lamellar structure " intercalation ", this is Nano tube array of titanium dioxide
Close-packed arrays are grown on the bracket in forming bracket, sheet Ni-Co double-metal hydroxide on titanium silk matrix, the bottom
Laminated structure be embedded in nanotube gap, the Ni-Co LDH for seeing two-dimensional slice stratiform that can be will be apparent that.
Electrochemical property test method of the present invention are as follows: by the TiO2NTs/Ni-Co LDH composite material of preparation
As electrode and its chemical property is tested, the chemical property of working electrode tests completion, electrolyte in three-electrode system
It is to electrode with platinized platinum, with saturated calomel electrode (SCE) for reference electrode, this three-electrode system is connected to for 1M KOH solution
On electrochemical workstation, using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing
The chemical property of electrode, cyclical stability test carry out on blue electric battery test system.As shown in Fig. 2, wherein (a) is to retouch
Cyclic voltammetry (cv) figure for stating the electrode material under different anodic oxidation voltages compares multiple under three kinds of anodic oxidation voltages
The CV curve of composite electrode, it is possible to find CV curve institute's envelope surface product is maximum when 50V, this shows under the anodic oxidation voltage of 50V, compound
The specific capacitance of electrode is maximum；(b) in Fig. 2 is for the impedance comparison of the made combination electrode of different anodic oxidation voltages, three songs
Line is made of semicircle and an oblique line, this illustrates the electrode process of TiO2NTs/Ni-Co LDH combination electrode by charge transfer
It is controlled simultaneously with diffusion process.When anodic oxidation voltage is 65V, half circular diameter of gained TiO2NTs/Ni-Co LDH combination electrode
Much smaller than both other, illustrate its charge-transfer resistance minimum, since its intersection point with X-axis is near zero point, therefore internal resistance also phase
To smaller, numerical value is about 1.8 Ω.When anodic oxidation voltage is 50V, the internal resistance of gained combination electrode is maximum；Anodic oxidation voltage is
When 80V, charge-transfer resistance is maximum.The diffusion process of the test curve reaction electrode material of low frequency part, corresponding impedance
Size is related with the slope of oblique line.In this figure, electrode obtained, corresponding oblique line portion incline when anodic oxidation voltage is 65V
Rake angle is slightly larger than in addition the two, so diffusion impedance is also smaller.In summary it discusses, anodic oxidation voltage is formed when being 65V
TiO2 nanotube and the electrode impedance that is compounded to form of Ni-Co double-metal hydroxide it is minimum.
(c) in Fig. 2 is that the cyclical stability of the made combination electrode of the method for the present invention under different anodic oxidation voltages compares,
After 2000 circle charge and discharge cycles, when anodic oxidation voltage 50V, 65V, 80V the circulation conservation rate of corresponding combination electrode distinguish
It is 80%, 88%, 58%.As it can be seen that TiO2NTs/Ni-Co LDH combination electrode obtained under 65V anodic oxidation voltage, is recycling
Possess absolute advantage in stability；(d) in Fig. 2 reflects the high rate performance of these three combination electrodes, when current density by
When 2mA/cm2 increases to 10mA/cm2, the specific capacitance of three has decline.Although anodic oxidation voltage is 50V, corresponding ratio
Capacitor highest, but TiO2NTs/Ni-Co LDH combination electrode when 65V, the decline of specific capacitance but the most slowly, only have dropped
21%.Therefore, in summary, Ni-Co double-metal hydroxide combination electrode prepared by the present invention has excellent electricity
Chemical property.
Claims (5)
1. a kind of titanium dioxide/double-metal hydroxide combination electrode preparation method, which comprises the following steps:
(1) high-purity titanium silk is cut to several segments that average length is 10cm, is sequentially placed into dilute hydrochloric acid solution, deionized water
Be respectively cleaned by ultrasonic 10min in dehydrated alcohol, be then placed into 70 DEG C of vacuum ovens it is 5-9 hours dry after pass through anodic oxygen
Change synthesizes TiO on titanium silk2NTs, the electrolyte solution used are 0.4%NH4F, the ethylene glycol solution of 10%vol deionized water；
(2) it is cleaned and dried the TiO of synthesis2NTs, being polarised improves its electric conductivity, i.e., will be obtained in step (1)
TiO2NTs is placed in the Na of 0.5mol/L2SO4It polarizes in solution, polarizing voltage is -1.5V, polarization time 3min；
(3) deposition liquid needed for preparing electrochemical deposition nickel salt, cobalt salt, ammonium chloride and deionized water is mixed；
(4) deposition liquid obtained by step (3) is placed in a beaker by starting electrochemical workstation, with TiO2NTs collector is work electricity
Pole, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under to TiO2NTs uses chronoptentiometry
Electrochemical deposition successively uses deionized water after reaction, and dehydrated alcohol cleans more than three times repeatedly, and dry in vacuum
10-12h is dried in dry case under the conditions of 70 DEG C of temperature, obtains TiO later2NTs/Ni-Co LDH combination electrode.
2. a kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode according to claim 1, feature
It is, the anodic oxidation condition in step (1) is voltage 50-80V, oxidization time 1-2h.
3. a kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode according to claim 2, feature
It is, the cobalt salt in step (3) is Co (NO3)2·6H2O, nickel salt are Ni (NO3)2·6H2O。
4. a kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode according to claim 1 or 2,
Be characterized in that, the electrolyte in step (3) by 2mmol Co (NO3)2·6H2O, the Ni (NO of 2-6mmol3)2·6H2O and
The NH of 20mmol4Cl, which is dissolved in 100mL deionized water, to be formulated.
5. a kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode according to claim 1 or 2,
It is characterized in that, the condition of the chronoptentiometry electrochemical deposition in step (4) is deposition current 0.01-0.02A, deposits duration
900s。
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