CN105513831A - Electrode material in hollow tubular structure, and preparation method for electrode material - Google Patents
Electrode material in hollow tubular structure, and preparation method for electrode material Download PDFInfo
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- CN105513831A CN105513831A CN201510813390.9A CN201510813390A CN105513831A CN 105513831 A CN105513831 A CN 105513831A CN 201510813390 A CN201510813390 A CN 201510813390A CN 105513831 A CN105513831 A CN 105513831A
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- copper
- kocide
- tubular structure
- hollow tubular
- complex hydroxide
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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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- 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 invention provides an electrode material in a hollow tubular structure, and the electrode material is in the hollow tubular structure which consists of a composite hydroxide/copper hydroxide/copper-contained metal substrate. The chemical formulation of the composite hydroxide is MxM'y(OH)2, wherein M is Ni2+ or Co2+, M' is Co2+, Al3+, or Fe3+. According to the invention, a method of solution dipping and constant potential deposition, and a copper hydroxide nanowire array grows on the copper-contained metal substrate in an in-situ manner. The composite hydroxide is deposited on a copper hydroxide nanorod in electrolyte containing mixed metal salt solution in a manner of electro-deposition through employing the method of constant potential deposition. Meanwhile, electrochemical corrosion enables the copper hydroxide nanorod to be dissolved in a process of electro-deposition, thereby obtaining the hollow tubular structure of the composite hydroxide/copper hydroxide/copper-contained metal substrate. The electrode material is good in super-capacitance performance, and can be used for a super-capacitor.
Description
Technical field:
The present invention relates to a kind of hollow tubular structure electrode material and preparation method thereof, be specifically related to complex hydroxide/Kocide SD/copper-containing metal substrate hollow tubular structure electrode material and preparation method thereof.
Background technology:
In the past few decades, people take a large amount of effort go design and build novel energy storage device.Ultracapacitor, due to its high-energy-density, good cyclical stability and efficiently charge-discharge performance, more and more get more and more people's extensive concerning.Research finds, in order to obtain desirable electrochemical capacitance performance, we must consider two aspects: the load capacity of electroactive component and charge transfer process (comprising the ion in electrolyte and the electronics in redox reaction).The research of one-dimensional nano line nucleocapsid structure makes electrode material for super capacitor burst out again unlimited life.Due to nucleocapsid structure possessed bigger serface shell and by the core of nano wire by multiple advantages such as collector and active component firmly combine, make solution specific surface that 1-dimention nano nucleocapsid structure can be comparatively satisfactory and load capacity two problems, thus be expected to the comparatively ideal ratio capacitance value of acquisition one.
Present stage, of common occurrence as the report of electrode material for super capacitor for 1-dimention nano nucleocapsid structure.The people such as poplar [NanoEnergy (2014) 7,170 – 178] and Ning Dengren [NanoEnergy (2014) 7,134 – 142] report Co respectively
3o
4niO nanometer rods nucleocapsid structure and Co
3o
4lDH nano-array, and achieve the higher ratio capacitance value of 2033F/g and 1722F/g.But the high rate performance of this kind of electrode material is not very well, only has 54.0% and 61.4% respectively, which limits the application of these electrode materials in actual production life.
In fact, electrochemical capacitance electrode material has good ratio capacitance value and relatively poor this phenomenon of high rate performance is much in scientific research.Nickel hydroxide nano wall has been prepared in the people such as land [Chem.Commun, 2011,47,9651 – 9653] success in foam nickel base, and obtains 7.83F/cm
2comparatively high specific capacitance value, but along with the increase of current density, the ratio capacitance value of this electrode material is reduced to 43.0% of initial value.Under normal circumstances, when the raising density of charging current, its ratio capacitance value can significantly lower, and showing is exactly that the high rate performance of electrode material is poor.Return and make a thorough investigation of the end, this is because at higher current densities, the electron transfer rate in electro-chemical activity site can not lead over that the conversion rate of redox reaction causes.In other words, although nanometer nuclear shell nano-structure is conducive to OH
-with electronics in electrolyte and interelectrode transmission, but this is nowhere near, and we also must improve the transmission efficiency between them, could improve the high rate performance of electrode material like this.Therefore, we wish that the electrode building a kind of hollow tubular nanometer nuclear shell nano-structure solves this problem.On the one hand, multistage shell can increase the specific area of electrode material, and promote the load capacity of active component, on the other hand, hollow tubular structure can allow electrolyte diffusion enter in nanotube, shortens electron diffusion path, effective transfer of accelerated charge.
For the shell of multilevel hierarchy, metal oxide/hydroxide, comprises NiAl-LDHs, NiTi-LDHs, Co
3o
4, NiO, Ni (OH)
2, Co (OH)
2it may be best selection.Wherein, Ni (OH)
2, Co (OH)
2because the layer structure of higher theoretical ratio capacitance value, feature redox reaction and uniqueness, and be widely used in the electrode material of fake capacitance capacitor.Meanwhile, consider the cooperative effect of hybrid metal ion, complex hydroxide is expected to be widely applied in the preparation of electrode material for super capacitor.
Summary of the invention:
The object of this invention is to provide a kind of hollow tubular structure electrode material and preparation method thereof, this material can be used as the electrode material of the energy storage device such as ultracapacitor, lithium battery.
Hollow tubular structure electrode material of the present invention is the hollow tubular structure material be made up of complex hydroxide/Kocide SD/copper-containing metal substrate, and wherein complex hydroxide chemical formulation is M
xm '
y(OH)
2, wherein M, M ' is two kinds of different metal ions, and wherein M is Ni
2+or Co
2+, M ' is Co
2+, Al
3+or Fe
3+.This material has unique microstructure, and wherein Kocide SD nanorod growth is in copper-containing metal substrate, the hollow tubular structure that complex hydroxide growth is formed at Kocide SD nanometer rods outer wall.
The present invention adopts the method for solution impregnation and potentiostatic electrodeposition, first growth in situ Kocide SD nano-wire array in copper-containing metal substrate, then in the electrolyte containing mixed salt solution, by the method for constant potential electro-deposition, complex hydroxide on Kocide SD nanometer rods substrates, simultaneously due to electrochemical corrosion effect, make in electrodeposition process, there is dissolution phenomena in Kocide SD nanometer rods, thus obtains complex hydroxide/Kocide SD/copper-containing metal substrate hollow tubular structure.This electrode material has good electrochemical capacitance performance, can be applicable to electrode material for super capacitor.
The preparation method of hollow tubular structure electrode material of the present invention, concrete steps are as follows:
A. impregnated in NaOH and ammonium persulfate mixed solution by pretreated copper-containing metal substrate, wherein the concentration of NaOH is 0.5-10.0mol/L, and the concentration of ammonium persulfate is 0.05-1.00mol/L; Take out after dipping 20-30min, clean with deionized water rinsing, be placed in 30-80 DEG C of baking oven dry, namely obtain the substrate that grown Kocide SD in copper-containing metal substrate.The Kocide SD grown is nano bar-shape structure, and described copper-containing metal substrate is the cupric elemental metallic material such as foam copper, copper sheet, copper mesh, copper alloy.
B. using Kocide SD/copper-containing metal substrate of obtaining in steps A as work electrode, be to electrode with Pt, Ag/AgCl is reference electrode, in mixed salt solution, electromotive force is potentiostatic electrodeposition 150-400 second under-0.9 ~-1.1V condition, obtains complex hydroxide/Kocide SD/copper-containing metal substrate tubular structure.
Described mixed salt solution is the mixing salt solution that M salt and M ' salt form, and wherein M is metal ion Ni
2+or Co
2+, M ' is metal ion Co
2+, Al
3+or Fe
3+; The anion of above-mentioned two kinds of salt has at least one to be NO
3 -, another kind is NO
3 -, Cl
-or SO
4 2-.In mixed salt solution, the mol ratio of M salt and M ' salt is 1 ~ 4:1, and total concentration of metal ions is 0.005-0.100mol/L.
Complex hydroxide described in step B is Ni
xco
1-x(OH)
2, Ni
xal
2/3 (1-x)(OH)
2, Co
xal
2/3 (1-x)(OH)
2, Ni
xfe
2/3 (1-x)(OH)
2and Co
xfe
2/3 (1-x)(OH)
2complex hydroxide.
Feature of the present invention is: the one-dimensional nano line array built in copper-containing metal substrate, can increase the load capacity of active component complex hydroxide, thus the ratio capacitance value that acquisition one is ideal.Due to the factor such as unsteadiness of electrochemical corrosion effect and Kocide SD nanometer rods, in the process of potentiostatic electrodeposition complex hydroxide, cause the dissolving of Kocide SD nanometer rods, thus obtain the structure of hollow tubular, this hollow tubular structure is conducive to fully contacting of electrolyte and electro-chemical activity component, shorten the approach of electric charge diffusion, accelerate effective transfer of electronics, make this electrode material have good high rate performance.Therefore, this material is suitable for the electrode material being used as the energy storage device such as ultracapacitor, lithium battery.
Characterize and application experiment
Fig. 1 is that the scanning electron microscopy (SEM) of Kocide SD/foam copper that embodiment 1 step B obtains characterizes, as seen from the figure, Kocide SD nanometer rods grows on foam copper surface uniformly, the smooth surface of nanometer rods, its diameter is 150-250 nanometer, and length is 5-15 micron.
Fig. 2 is that the transmission electron microscope (TEM) of Kocide SD/foam copper that embodiment 1 step B obtains characterizes, and as seen from the figure, Kocide SD nanorod diameter is about 200 nanometers, and is solid construction.
Fig. 3 is that the X-ray diffraction (XRD) of nickel cobalt complex hydroxide/Kocide SD/foam copper that embodiment 1 step C obtains characterizes, as seen from the figure, except there is foam copper basement feature diffraction maximum (representing by " # "), have also appeared (001), (101) characteristic diffraction peak of (020), (021) of Kocide SD phase, (002) characteristic diffraction peak and nickel cobalt complex hydroxide, illustrate that this material is nickel cobalt complex hydroxide/Kocide SD/foam copper structure.
Fig. 4 is that the scanning electron microscopy (SEM) of nickel cobalt complex hydroxide/Kocide SD/foam copper that embodiment 1 step C obtains characterizes, as seen from the figure, nickel cobalt complex hydroxide nanometer sheet is wrapped in Kocide SD nanometer rods outer wall, forms tubulose multilevel hierarchy.
Fig. 5 is that the transmission electron microscope (TEM) of nickel cobalt complex hydroxide/Kocide SD/foam copper that embodiment 1 step C obtains characterizes, as seen from the figure, nickel cobalt complex hydroxide nanoscale twins thickness is about 50 nanometers, and the nickel cobalt complex hydroxide/Kocide SD/foam copper structure of formation is hollow structure.
Fig. 6 is that the scanning electron microscopy (SEM) after nickel cobalt complex hydroxide/Kocide SD/foam copper structural deterioration of obtaining of embodiment 1 step C characterizes, as seen from the figure, there is pore passage structure in nanometer rods section, confirms that the nickel cobalt complex hydroxide/Kocide SD/foam copper of preparation is hollow tubular structure further.
Fig. 7 is that the scanning electron microscopy (SEM) of ferronickel complex hydroxide/Kocide SD/foam copper that embodiment 3 step C obtains characterizes, as seen from the figure, ferronickel complex hydroxide/Kocide SD/the foam copper formed is hollow tubular structure, and its length is 5-15 micron.
Fig. 8 is that the scanning electron microscopy (SEM) of cobalt aluminum complex hydroxide/Kocide SD/foam copper that embodiment 5 step C obtains characterizes, as seen from the figure, cobalt aluminum complex hydroxide is attached to nanotube outer wall with graininess, and form tubulose multilevel hierarchy, nanotube length is 5-10 micron.
Fig. 9 is the cyclic voltammetry curve of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in the KOH electrolyte of 1mol/L that embodiment 1 step C obtains, and sweep speed is respectively 1mV/s, 5mV/s, 10mV/s, 20mV/s, 30mV/s.As seen from the figure, under 1mV/s low sweeps fast condition, there is redox character peak.But under height sweeps fast condition, redox character peak is not obvious, its reason may be that the oxidation-reduction potential of nickel cobalt is close, thus mutually caused by interference.
Figure 10 is the charging and discharging curve of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in the KOH electrolyte of 1mol/L under different current density that embodiment 1 step C obtains, charge and discharge process carries out between 0-0.4V, and capacitance can be obtained by following formulae discovery:
C represents ratio capacitance (F/g or F/cm
2), I is charging and discharging currents (mA), and Δ t is discharge and recharge time (s), and Δ V is voltage (V), m is the quality (g) of electrode active component, and A is electrode active component area occupied (1.0*1.0cm
2).5mA/cm is respectively in current density
2, 10mA/cm
2, 20mA/cm
2, 30mA/cm
2time, ratio capacitance value is respectively 22.125,21.445,19.840,17.394F/cm
2, its respective quality ratio capacitance value is respectively 1923.91,1864.78,1725.22,1512.52F/g (electrode active component is 0.0115g).
Figure 11 is the stable circulation linearity curve of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in the KOH electrolyte of 1mol/L that embodiment 1 step C obtains, as seen from the figure, at 30mA/cm
2high current densities under, 1000 circulation after still keep 86.68% capacity, illustrate that this material has long-time stability, can be used for ultracapacitor actual production life in.
Figure 12 is the charge-discharge magnification curve of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in the KOH electrolyte of 1mol/L that embodiment 1 step C obtains, and as seen from the figure, along with the increase of current density, ratio capacitance value lowers, along with current density is by 5mA/cm
2be increased to 30mA/cm
2, ratio capacitance value reduces to initial 78.62%, higher than the most of electrode materials reported at present.Illustrate that this electrode material still has ideal ratio capacitance value under high charge-discharge rate conditions, this illustrate unique hollow structure be conducive to electrolyte with active group understand fully contact, shorten the approach of charge transfer, accelerate charge transfer process, make this electrode material take into account the advantage of high specific capacitance value and high rate capability, be expected to effectively be applied in electrode material for super capacitor.
Beneficial effect of the present invention: the method adopting solution impregnation and constant potential electro-deposition, growth in situ Kocide SD nano-wire array in copper-containing metal substrate, and in Kocide SD nanometer rods potentiostatic electrodeposition complex hydroxide.Due to electrochemical corrosion effect, Kocide SD is dissolved, thus obtain the multilevel hierarchy of hollow tubular.The preparation of the method is simple, fast, with low cost, and the product structure obtained is good, and conductivity is strong, in addition, by controlling the potentiostatic electrodeposition time, can reach the object of pattern and the regulation and control complex hydroxide load capacity controlling material.Due to the structural advantage of this product, make this electrode material have good electrochemical capacitance performance (high, the stability of ratio capacitance value strong, good rate capability), it is expected to be with a wide range of applications in the electrode material of ultracapacitor and even other energy storage devices.
Accompanying drawing explanation
Fig. 1 is scanning electron microscopy (SEM) sign of the Kocide SD/foam copper in embodiment 1.
Fig. 2 is transmission electron microscope (TEM) sign of the Kocide SD/foam copper in embodiment 1.
Fig. 3 is X-ray diffraction (XRD) figure of the nickel cobalt complex hydroxide/Kocide SD/foam copper in embodiment 1.
Fig. 4 is scanning electron microscopy (SEM) sign of the nickel cobalt complex hydroxide/Kocide SD/foam copper in embodiment 1.
Fig. 5 is transmission electron microscope (TEM) sign of the nickel cobalt complex hydroxide/Kocide SD/foam copper in embodiment 1.
Fig. 6 is that the scanning electron microscopy (SEM) after the nickel cobalt complex hydroxide/Kocide SD/foam copper structural deterioration in embodiment 1 characterizes.
Fig. 7 is scanning electron microscopy (SEM) sign of the ferronickel complex hydroxide/Kocide SD/foam copper in embodiment 3.
Fig. 8 is scanning electron microscopy (SEM) sign of the cobalt aluminum complex hydroxide/Kocide SD/foam copper in embodiment 5.
Fig. 9 is the cyclic voltammetry curve of the nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1.
Figure 10 is the nickel cobalt complex hydroxide/Kocide SD/charging and discharging curve of foam copper electrode under different current density in embodiment 1.
Figure 11 is the stable circulation linearity curve of the nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1.
Figure 12 is the charge-discharge magnification curve of the nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1.
Embodiment
Embodiment 1
A. the preliminary treatment of foam copper.
Be greater than the foam copper of 90% with purity for raw material, be cut into as 4.0*3.0cm
2the sheet of size, with the hydrochloric ultrasonic wave cleaning 5min of 10%, then rinses well with deionized water and absolute ethyl alcohol respectively, puts into 60 DEG C of baking oven drying for standby.
The ammonium persulfate of the NaOH and 2.28g that B. take 10.0g is dissolved in the deionized water of 100mL, be made into the mixed solution that concentration is respectively 2.5mol/L and 0.1mol/L, take out in foam copper substrate complete for preliminary treatment dipping mixed solution after 20min, with deionized water rinsing, be placed in 60 DEG C of baking oven drying for standby, Kocide SD nanometer rods can be grown in foam copper substrate.
C. take the nickel nitrate of 2.18g and the cobalt nitrate of 2.18g, be dissolved in the deionized water of 50mL, as electrolyte solution.Kocide SD/the foam copper obtained by step B, as work electrode, is to electrode with Pt, and Ag/AgCl is reference electrode.Under-1.0V electrical potential conditions, potentiostatic electrodeposition 300 seconds, thus obtain Ni
0.5co
0.5(OH)
2nickel cobalt complex hydroxide/Kocide SD/foam copper tubular structure material.
Embodiment 2
A. select purity to be greater than the copper mesh of 99%, be cut into as 4.0*3.0cm
2the sheet of size, by the disposal methods of embodiment 1.
B. the NaOH of 5.0g and the ammonium persulfate of 1.85g is taken, be dissolved in the deionized water of 100mL, be made into mixed solution, copper mesh substrate complete for preliminary treatment be impregnated in mixed solution and take out after 25min, with deionized water rinsing, be placed in 60 DEG C of baking oven drying for standby.
C. take the cobalt nitrate of 1.09g and the iron chloride of 0.41g, be dissolved in the deionized water of 50mL, as electrolyte solution.Kocide SD/the copper mesh obtained by step B, as work electrode, is to electrode with Pt, and Ag/AgCl is reference electrode.Under-1.0V electrical potential conditions, potentiostatic electrodeposition 150 seconds, thus obtain Co
0.5fe
0.33(OH)
2ferro-cobalt complex hydroxide/Kocide SD/copper mesh tubular structure material.
Embodiment 3
A. with embodiment 1.
B. the NaOH of 5.0g and the ammonium persulfate of 1.44g is taken, be dissolved in the deionized water of 100mL, be made into mixed solution, foam copper substrate complete for preliminary treatment be impregnated in mixed solution and take out after 30min, with deionized water rinsing, be placed in 45 DEG C of baking oven drying for standby.
C. take the nickel nitrate of 1.09g and the ferric sulfate of 0.60g, be dissolved in the deionized water of 50mL, as electrolyte solution.Kocide SD/the foam copper obtained by step B, as work electrode, is to electrode with Pt, and Ag/AgCl is reference electrode.Under-1.1V electrical potential conditions, potentiostatic electrodeposition 200 seconds, thus obtain Ni
0.625fe
0.25(OH)
2ferronickel complex hydroxide/Kocide SD/foam copper hollow tubular structure material.
Embodiment 4
A. select purity to be greater than the copper sheet of 90%, be cut into as 4.0*3.0cm
2the sheet of size, with the method process of embodiment 1.
B. the NaOH of 8.0g and the ammonium persulfate of 2.0g is taken, be dissolved in the deionized water of 100mL, be made into mixed solution, copper sheet substrate complete for preliminary treatment be impregnated in mixed solution and take out after 25min, with deionized water rinsing, be placed in 60 DEG C of baking oven drying for standby.
C. take the nickel nitrate of 2.91g and the aluminum sulfate of 1.67g, be dissolved in the deionized water of 50mL, as electrolyte solution.Kocide SD/the copper sheet obtained by step B, as work electrode, is to electrode with Pt, and Ag/AgCl is reference electrode.Under-0.9V electrical potential conditions, potentiostatic electrodeposition 250 seconds, thus obtain Ni
0.73al
0.18(OH)
2nickel aluminum complex hydroxide/Kocide SD/copper sheet tubular structure material.
Embodiment 5
A. with embodiment 1.
B. the NaOH of 10.0g and the ammonium persulfate of 2.28g is taken, be dissolved in the deionized water of 100mL, be made into mixed solution, foam copper substrate complete for preliminary treatment be impregnated in mixed solution and take out after 20min, with deionized water rinsing, be placed in 30 DEG C of baking oven drying for standby.
C. take the cobalt nitrate of 2.18g and the aluminum nitrate of 0.94g, be dissolved in the deionized water of 50mL, as electrolyte solution.Kocide SD/the foam copper obtained by step B, as work electrode, is to electrode with Pt, and Ag/AgCl is reference electrode.Under-1.0V electrical potential conditions, potentiostatic electrodeposition 250 seconds, thus obtain Co
0.67al
0.22(OH)
2cobalt aluminum complex hydroxide/Kocide SD/foam copper tubular structure material.
Claims (3)
1. a preparation method for hollow tubular structure electrode material, concrete steps are as follows:
A. impregnated in NaOH and ammonium persulfate mixed solution by pretreated copper-containing metal substrate, wherein the concentration of NaOH is 0.5-10.0mol/L, and the concentration of ammonium persulfate is 0.05-1.00mol/L; Take out after dipping 20-30min, clean with deionized water rinsing, be placed in 30-80 DEG C of baking oven dry, namely obtain the substrate that grown Kocide SD in copper-containing metal substrate; The Kocide SD grown is nano bar-shape structure; Described copper-containing metal substrate is foam copper, copper sheet, one of copper mesh or copper alloy;
B. Kocide SD steps A obtained/copper-containing metal substrate is as work electrode, be to electrode with Pt, Ag/AgCl is reference electrode, in mixed salt solution, electromotive force is potentiostatic electrodeposition 150-400 second under-0.9 ~-1.1V condition, obtains complex hydroxide/Kocide SD/copper-containing metal substrate tubular structure;
Mixed salt solution described in step B is the mixing salt solution that M salt and M ' salt form, and wherein M is metal ion Ni
2+or Co
2+, M ' is metal ion Co
2+, Al
3+or Fe
3+, and be Co when M and M ' is different
2+; The anion of above-mentioned two kinds of salt has at least one to be NO
3 -, another kind is NO
3 -, Cl
-or SO
4 2-; In mixed salt solution, the mol ratio of M salt and M ' salt is 1 ~ 4:1, and total concentration of metal ions is 0.005-0.100mol/L;
Complex hydroxide described in step B is Ni
xco
1-x(OH)
2, Ni
xal
2/3 (1-x)(OH)
2, Co
xal
2/3 (1-x)(OH)
2, Ni
xfe
2/3 (1-x)(OH)
2and Co
xfe
2/3 (1-x)(OH)
2complex hydroxide, it is the structure of hollow tubular.
2. the hollow tubular structure electrode material prepared of method according to claim 1, it is the hollow tubular structure material be made up of complex hydroxide/Kocide SD/copper-containing metal substrate, and wherein complex hydroxide chemical formulation is M
xm '
y(OH)
2, wherein M is Ni
2+or Co
2+, M ' is Co
2+, Al
3+or Fe
3+, and be Co when M and M ' is different
2+.
3. hollow tubular structure electrode material according to claim 2, is characterized in that this material microstructure is; Kocide SD nanorod growth is in copper-containing metal substrate, and complex hydroxide growth is at the hollow tubular structure of Kocide SD nanometer rods outer wall formation.
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