CN105513831B - A kind of hollow tubular structure electrode material and preparation method thereof - Google Patents
A kind of hollow tubular structure electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN105513831B CN105513831B CN201510813390.9A CN201510813390A CN105513831B CN 105513831 B CN105513831 B CN 105513831B CN 201510813390 A CN201510813390 A CN 201510813390A CN 105513831 B CN105513831 B CN 105513831B
- Authority
- CN
- China
- Prior art keywords
- copper
- kocide
- metal substrate
- containing metal
- tubular structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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 a kind of hollow tubular structure electrode material, it is the hollow tubular structure material being made up of complex hydroxide/Kocide SD/copper-containing metal substrate, and wherein complex hydroxide chemical formula is expressed as MxM’y(OH)2, wherein M is Ni2+Or Co2+, M ' is Co2+、Al3+Or Fe3+.The present invention impregnates the method with potentiostatic electrodeposition using solution, the first growth in situ Kocide SD nano-wire array in copper-containing metal substrate, then in the electrolyte containing mixed salt solution, with the method for constant potential electro-deposition, the complex hydroxide in electro-deposition in Kocide SD nanometer rods, simultaneously because electrochemical corrosion is acted on so that in electrodeposition process, there is dissolution phenomena in Kocide SD nanometer rods, so as to obtain complex hydroxide/Kocide SD/copper-containing metal substrate hollow tubular structure.The electrode material has good electrochemical capacitance performance, can be applied to electrode material for super capacitor.
Description
Technical field：
The present invention relates to a kind of hollow tubular structure electrode material and preparation method thereof, and in particular to and 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 substantial amounts of effort and go to design and build new energy storage device.It is super
Capacitor, due to its high-energy-density, preferable cyclical stability and efficient charge-discharge performance, increasingly by people's
Extensive concern.Research is found, in order to obtain preferable electrochemical capacitance performance, we must consider that two aspects：Electroactive component
Load capacity and charge transfer process (including electronics in the ion and redox reaction in electrolyte).One-dimensional nano line
The research of core shell structure causes electrode material for super capacitor to burst out unlimited life again.Because core shell structure possesses big ratio
The shell of surface area and collector and active component are firmly combined together etc. by multiple advantage by the core of nano wire so that one
Tie up nano-core-shell structure can more satisfactory solution than two problems in surface and load capacity so that be expected to obtain one it is more satisfactory
Specific capacitance value.
At this stage, it is of common occurrence as the report of electrode material for super capacitor for 1-dimention nano core shell structure.Poplar
Et al. [Nano Energy (2014) 7,170-178] and peaceful et al. [Nano Energy (2014) 7,134-142] report respectively
Co3O4@NiO nanometer rods core shell structures and Co3O4@LDH nano-arrays, and achieve 2033F/g and 1722F/g is higher
Specific capacitance value.But, the high rate performance of this kind of electrode material be not it is fine, respectively only 54.0% and 61.4%, this will limit
Application of these electrode materials in actual production life is made.
In fact, electrochemical capacitance electrode material has good specific capacitance value and this relatively poor phenomenon of high rate performance exists
It is much in scientific research.Land et al. [Chem.Commun, 2011,47,9651-9653] success is made in foam nickel base
It is standby gone out nickel hydroxide nano wall, and obtain 7.83F/cm2Relatively high specific capacitance value, but with the increase of current density, the electricity
The specific capacitance value of pole material is reduced to the 43.0% of initial value.Under normal circumstances, when the density of charging current is improved, it compares
Capacitance can significantly lower, show be exactly electrode material high rate performance it is poor.Return thorough investigation bottom, because close in high current
Under degree, the electron transfer rate in electro-chemical activity site can not be led over caused by the conversion rate of redox reaction.
In other words, although nanometer nuclear shell nano-structure is conducive to OH-With electronics in electrolyte and interelectrode transmission, but this is far from
Enough, we must also improve the transmission efficiency between them, could so improve the high rate performance of electrode material.Therefore, we
Wish to build a kind of electrode of hollow tubular nanometer nuclear shell nano-structure to solve this problem.On the one hand, multistage shell can increase
The specific surface area of electrode material, lifts the load capacity of active component, on the other hand, hollow tubular structure can allow electrolyte diffusion
Enter in nanotube, shorten electron diffusion path, effective transfer of accelerated charge.
For the shell of multilevel hierarchy, metal oxide/hydroxide, including NiAl-LDHs, NiTi-LDHs, Co3O4,
NiO,Ni(OH)2,Co(OH)2It is probably optimal selection.Wherein, Ni (OH)2,Co(OH)2Because higher theoretical specific capacitance
The layer structure of value, feature redox reaction and uniqueness, and it is widely used in the electrode material of fake capacitance capacitor.Together
When, it is contemplated that the cooperative effect of hybrid metal ion, complex hydroxide is expected to be widely applied to electrode of super capacitor material
In the preparation of material.
The content of the invention：
It is an object of the invention to provide a kind of hollow tubular structure electrode material and preparation method thereof, the material can be used as surpassing
The electrode material of the energy storage devices such as level capacitor, lithium battery.
Hollow tubular structure electrode material of the present invention is by complex hydroxide/Kocide SD/copper-containing metal base
The hollow tubular structure material that bottom is constituted, wherein complex hydroxide chemical formula is expressed as MxM’y(OH)2, wherein M, M ' is two kinds
Different metal ions, wherein M are Ni2+Or Co2+, M ' is Co2+、Al3+Or Fe3+.The material has unique microstructure, wherein
Kocide SD nanorod growth is in copper-containing metal substrate, and complex hydroxide is grown in the formation of Kocide SD nanometer rods outer wall
Hollow tubular structure.
The present invention impregnates the method with potentiostatic electrodeposition using solution, first the growth in situ hydroxide in copper-containing metal substrate
Arrays of Copper Nanowires, then in the electrolyte containing mixed salt solution, with the method for constant potential electro-deposition, in Kocide SD
Complex hydroxide in electro-deposition in nanometer rods, simultaneously because electrochemical corrosion is acted on so that in electrodeposition process, hydroxide
There is dissolution phenomena in copper nanometer rods, so as to obtain complex hydroxide/Kocide SD/copper-containing metal substrate hollow tubular structure.
The electrode material has good electrochemical capacitance performance, can be applied to electrode material for super capacitor.
The preparation method of hollow tubular structure electrode material of the present invention, is comprised the following steps that：
A. pretreated copper-containing metal substrate is impregnated in sodium hydroxide and ammonium persulfate mixed solution, wherein hydrogen-oxygen
The concentration for changing sodium is 0.5-10.0mol/L, and the concentration of ammonium persulfate is 0.05-1.00mol/L；Impregnate and taken out after 20-30min,
Rinsed well with deionized water, be placed in 30-80 DEG C of baking oven and dry, that is, obtain grown Kocide SD in copper-containing metal substrate
Substrate.The Kocide SD grown is nano bar-shape structure, and described copper-containing metal substrate is foam copper, copper sheet, copper mesh, copper
The cupric elemental metallic material such as alloy.
B. using the Kocide SD obtained in step A/copper-containing metal substrate as working electrode, using Pt as to electrode, Ag/
AgCl is reference electrode, in mixed salt solution, and potential is potentiostatic electrodeposition 150-400 seconds under the conditions of -0.9~-1.1V,
Obtain complex hydroxide/Kocide SD/copper-containing metal substrate tubular structure.
Described mixed salt solution is the mixing salt solution of M salt and M ' salt composition, and wherein M is metal ion Ni2+Or
Co2+, M ' is metal ion Co2+、Al3+Or Fe3+；The anion of above two salt at least one kind is NO3 -, another is NO3 -、
Cl-Or SO4 2-.In mixed salt solution, the mol ratio of M salt and M ' salt is 1~4:1, total concentration of metal ions is 0.005-
0.100mol/L。
Complex hydroxide described in step B is NixCo1-x(OH)2、NixAl2/3(1-x)(OH)2、CoxAl2/3(1-x)(OH)2、
NixFe2/3(1-x)(OH)2And CoxFe2/3(1-x)(OH)2Complex hydroxide.
It is characteristic of the invention that：The one-dimensional nano line array built in copper-containing metal substrate, by increasing capacitance it is possible to increase active component
The load capacity of complex hydroxide, so as to obtain an ideal specific capacitance value.Due to electrochemical corrosion effect and hydrogen
The factors such as the unstability of cupric oxide nano-rod, during potentiostatic electrodeposition complex hydroxide, cause Kocide SD
The dissolving of nanometer rods, so as to obtain the structure of hollow tubular, this hollow tubular structure is conducive to electrolyte and electro-chemical activity
The abundant contact of component, shorten electric charge diffusion approach, accelerate effective transfer of electronics so that the electrode material have compared with
Good high rate performance.Therefore, the material is adapted for use as the electrode material of the energy storage devices such as ultracapacitor, lithium battery.
Characterize and application experiment
Fig. 1 is that the SEM (SEM) for Kocide SD/foam copper that the step B of embodiment 1 is obtained is characterized, by scheming
It can be seen that, Kocide SD nanometer rods are uniformly grown in foam copper surface, and the surface of nanometer rods is smooth, and its a diameter of 150-250 receives
Rice, length is 5-15 microns.
Fig. 2 is that the transmission electron microscope (TEM) for Kocide SD/foam copper that the step B of embodiment 1 is obtained is characterized, by scheming
It can be seen that, Kocide SD nanorod diameter is about 200 nanometers, and is solid construction.
Fig. 3 is the X-ray diffraction for nickel cobalt complex hydroxide/Kocide SD/foam copper that the step C of embodiment 1 is obtained
(XRD) characterize, as seen from the figure, in addition to there is foam copper basement feature diffraction maximum (being represented with " # "), have also appeared Kocide SD
(001), (101) characteristic diffraction peak of (020), (021) of phase, (002) characteristic diffraction peak and nickel cobalt complex hydroxide, says
The bright material is nickel cobalt complex hydroxide/Kocide SD/foam steel structure.
Fig. 4 is the scanning electron microscopy for nickel cobalt complex hydroxide/Kocide SD/foam copper that the step C of embodiment 1 is obtained
Mirror (SEM) is characterized, as seen from the figure, and nickel cobalt complex hydroxide nanometer sheet is wrapped in Kocide SD nanometer rods outer wall, forms tubulose
Multilevel hierarchy.
Fig. 5 is the transmission electron microscopy for nickel cobalt complex hydroxide/Kocide SD/foam copper that the step C of embodiment 1 is obtained
Mirror (TEM) is characterized, and as seen from the figure, nickel cobalt complex hydroxide nanoscale twins thickness is about 50 nanometers, and the nickel cobalt of formation is combined hydrogen
Oxide/Kocide SD/foam steel structure is hollow structure.
Fig. 6 is sweeping after nickel cobalt complex hydroxide/Kocide SD/foam steel structure that the step C of embodiment 1 is obtained is destroyed
Electron microscope (SEM) sign is retouched, as seen from the figure, pore passage structure occurs in nanometer rods section, further confirm that the nickel cobalt prepared is answered
Conjunction hydroxide/Kocide SD/foam copper is hollow tubular structure.
Fig. 7 is the scanning electron microscopy for ferronickel complex hydroxide/Kocide SD/foam copper that the step C of embodiment 3 is obtained
Mirror (SEM) is characterized, as seen from the figure, and ferronickel complex hydroxide/Kocide SD/foam copper of formation is hollow tubular structure, its
Length is 5-15 microns.
Fig. 8 is the scanning electron microscopy for cobalt aluminum complex hydroxide/Kocide SD/foam copper that the step C of embodiment 5 is obtained
Mirror (SEM) is characterized, as seen from the figure, and cobalt aluminum complex hydroxide is attached to a nanometer pipe outer wall with graininess, forms tubulose multistage knot
Structure, nanotube length is 5-10 microns.
Fig. 9 is the obtained nickel cobalt complex hydroxide/Kocide SD/foam copper electrodes of the step C of embodiment 1 in 1mol/L
Cyclic voltammetry curve in KOH electrolyte, sweep speed is respectively 1mV/s, 5mV/s, 10mV/s, 20mV/s, 30mV/s.By scheming
It can be seen that, 1mV/s it is low sweep speed under the conditions of, occur in that redox character peak.But under the conditions of height sweeps speed, redox character
Peak is not obvious, and its reason may be close for the oxidation-reduction potential of nickel cobalt, so that caused by interfering.
Figure 10 is the obtained nickel cobalt complex hydroxide/Kocide SD/foam copper electrodes of the step C of embodiment 1 in 1mol/L
KOH electrolyte in charging and discharging curve under different current densities, charge and discharge process is carried out between 0-0.4V, and capacitance can
Obtained with being calculated by below equation：
Or
C represents specific capacitance (F/g or F/cm2), I is charging and discharging currents (mA), and Δ t is the discharge and recharge time (s), and Δ V is electricity
Press (V), m is the quality (g) of electrode active component, and A is electrode active component occupied area (1.0*1.0cm2).In current density
Respectively 5mA/cm2、10mA/cm2、20mA/cm2、30mA/cm2When, specific capacitance value is respectively 22.125,21.445,19.840,
17.394F/cm2, its respective quality specific capacitance value is respectively 1923.91,1864.78,1725.22,1512.52F/g (electrode actives
Property component be 0.0115g).
Figure 11 is the obtained nickel cobalt complex hydroxide/Kocide SD/foam copper electrodes of the step C of embodiment 1 in 1mol/L
KOH electrolyte in stable circulation linearity curve, as seen from the figure, in 30mA/cm2High current densities under, 1000
Still kept after individual circulation 86.68% capacity, illustrate that the material has long-time stability, available for ultracapacitor actual production
In life.
Figure 12 is the obtained nickel cobalt complex hydroxide/Kocide SD/foam copper electrodes of the step C of embodiment 1 in 1mol/L
KOH electrolyte in charge-discharge magnification curve, as seen from the figure, with the increase of current density, specific capacitance value lowers, with electricity
Current density is by 5mA/cm2Increase to 30mA/cm2, specific capacitance value is reduced to initial 78.62%, most of higher than what is reported at present
Electrode material.Illustrate that the electrode material still has ideal specific capacitance value under high charge-discharge rate conditions, this explanation is only
Special hollow structure is conducive to electrolyte fully to be contacted with what activearm was understood, shortens the approach of charge transfer, accelerates electric charge
Transfer process so that the electrode material has taken into account high specific capacitance value and the advantage of high rate capability, is expected in super capacitor electrode
Effectively applied in the material of pole.
Beneficial effects of the present invention：Method with constant potential electro-deposition is impregnated using solution, it is former in copper-containing metal substrate
Position growth Kocide SD nano-wire array, and the potentiostatic electrodeposition complex hydroxide in Kocide SD nanometer rods.Due to electrification
Learn corrosiveness so that Kocide SD dissolves, so as to obtain the multilevel hierarchy of hollow tubular.The preparation of this method is simple,
Quickly, with low cost, and the product structure obtained is good, electric conductivity is strong, in addition, by controlling the potentiostatic electrodeposition time, can be with
Reach the pattern of control material and the purpose of regulation and control complex hydroxide load capacity.Due to the structural advantage of the product so that should
Electrode material has preferable electrochemical capacitance performance (specific capacitance value is high, stability is strong, good rate capability), and it is expected in super capacitor
It is with a wide range of applications in the electrode material of device or even other energy storage devices.
Brief description of the drawings
Fig. 1 is that the SEM (SEM) of Kocide SD/foam copper in embodiment 1 is characterized.
Fig. 2 is that the transmission electron microscope (TEM) of Kocide SD/foam copper in embodiment 1 is characterized.
Fig. 3 is X-ray diffraction (XRD) figure of nickel cobalt complex hydroxide/Kocide SD/foam copper in embodiment 1.
Fig. 4 is the SEM (SEM) of nickel cobalt complex hydroxide/Kocide SD/foam copper in embodiment 1
Characterize.
Fig. 5 is the transmission electron microscope (TEM) of nickel cobalt complex hydroxide/Kocide SD/foam copper in embodiment 1
Characterize.
Fig. 6 is the scanning electron after nickel cobalt complex hydroxide/Kocide SD/foam steel structure destruction in embodiment 1
Microscope (SEM) is characterized.
Fig. 7 is the SEM (SEM) of ferronickel complex hydroxide/Kocide SD/foam copper in embodiment 3
Characterize.
Fig. 8 is the SEM (SEM) of cobalt aluminum complex hydroxide/Kocide SD/foam copper in embodiment 5
Characterize.
Fig. 9 is the cyclic voltammetry curve of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1.
Figure 10 is nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1 under different current densities
Charging and discharging curve.
Figure 11 is that the cyclical stability of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1 is bent
Line.
Figure 12 is that the charge-discharge magnification of nickel cobalt complex hydroxide/Kocide SD/foam copper electrode in embodiment 1 is bent
Line.
Embodiment
Embodiment 1
A. the pretreatment of foam copper.
Using foam copper of the purity more than 90% as raw material, it is cut into as 4.0*3.0cm2The piece of size, with 10% salt
Acid is cleaned by ultrasonic 5min, is then rinsed well respectively with deionized water and absolute ethyl alcohol, is put into drying for standby in 60 DEG C of baking ovens.
B. the ammonium persulfate of the sodium hydroxide and 2.28g that weigh 10.0g is dissolved in 100mL deionized water, is made into dense
Degree is respectively 2.5mol/L and 0.1mol/L mixed solution, and the foam copper substrate pre-processed is impregnated in mixed solution
Taken out after 20min, with deionized water rinsing, be placed in drying for standby in 60 DEG C of baking ovens, you can grow hydrogen in foam copper substrate
Cupric oxide nano-rod.
C. 2.18g nickel nitrate and 2.18g cobalt nitrate are weighed, is dissolved in 50mL deionized water, electrolyte is used as
Solution.Kocide SD/foam copper that step B is obtained is as working electrode, and using Pt as to electrode, Ag/AgCl is reference electrode.
Under -1.0V electrical potential conditions, potentiostatic electrodeposition 300 seconds, so as to obtain Ni0.5Co0.5(OH)2Nickel cobalt complex hydroxide/hydrogen-oxygen
Change copper/foam copper tubular structure material.
Embodiment 2
A. it is more than 99% copper mesh from purity, is cut into as 4.0*3.0cm2The piece of size, with the processing of embodiment 1
Method processing.
B. 5.0g sodium hydroxide and 1.85g ammonium persulfate are weighed, is dissolved in 100mL deionized water, is made into mixed
Solution is closed, the copper mesh substrate pre-processed is impregnated in mixed solution after 25min and taken out, with deionized water rinsing, 60 are placed in
Drying for standby in DEG C baking oven.
C. 1.09g cobalt nitrate and 0.41g iron chloride are weighed, is dissolved in 50mL deionized water, electrolyte is used as
Solution.Kocide SD/copper mesh that step B is obtained is as working electrode, and using Pt as to electrode, Ag/AgCl is reference electrode.
Under -1.0V electrical potential conditions, potentiostatic electrodeposition 150 seconds, so as to obtain Co0.5Fe0.33(OH)2Ferro-cobalt complex hydroxide/hydrogen-oxygen
Change copper/copper mesh tubular structure material.
Embodiment 3
A. be the same as Example 1.
B. 5.0g sodium hydroxide and 1.44g ammonium persulfate are weighed, is dissolved in 100mL deionized water, is made into mixed
Solution is closed, the foam copper substrate pre-processed is impregnated in mixed solution after 30min and taken out, with deionized water rinsing, is placed in
Drying for standby in 45 DEG C of baking ovens.
C. 1.09g nickel nitrate and 0.60g ferric sulfate are weighed, is dissolved in 50mL deionized water, electrolyte is used as
Solution.Kocide SD/foam copper that step B is obtained is as working electrode, and using Pt as to electrode, Ag/AgCl is reference electrode.
Under -1.1V electrical potential conditions, potentiostatic electrodeposition 200 seconds, so as to obtain Ni0.625Fe0.25(OH)2Ferronickel complex hydroxide/hydrogen
Cupric oxide/foam copper hollow tubular structure material.
Embodiment 4
A. it is more than 90% copper sheet from purity, is cut into as 4.0*3.0cm2The piece of size, with the method for embodiment 1
Processing.
B. 8.0g sodium hydroxide and 2.0g ammonium persulfate are weighed, is dissolved in 100mL deionized water, mixing is made into
Solution, the copper sheet substrate pre-processed is impregnated in mixed solution after 25min and taken out, with deionized water rinsing, 60 DEG C are placed in
Drying for standby in baking oven.
C. 2.91g nickel nitrate and 1.67g aluminum sulfate are weighed, is dissolved in 50mL deionized water, electrolyte is used as
Solution.Kocide SD/copper sheet that step B is obtained is as working electrode, and using Pt as to electrode, Ag/AgCl is reference electrode.
Under -0.9V electrical potential conditions, potentiostatic electrodeposition 250 seconds, so as to obtain Ni0.73Al0.18(OH)2Nickel aluminum complex hydroxide/hydrogen-oxygen
Change copper/copper sheet tubular structure material.
Embodiment 5
A. be the same as Example 1.
B. 10.0g sodium hydroxide and 2.28g ammonium persulfate are weighed, is dissolved in 100mL deionized water, is made into mixed
Solution is closed, the foam copper substrate pre-processed is impregnated in mixed solution after 20min and taken out, with deionized water rinsing, is placed in
Drying for standby in 30 DEG C of baking ovens.
C. 2.18g cobalt nitrate and 0.94g aluminum nitrate are weighed, is dissolved in 50mL deionized water, electrolyte is used as
Solution.Kocide SD/foam copper that step B is obtained is as working electrode, and using Pt as to electrode, Ag/AgCl is reference electrode.
Under -1.0V electrical potential conditions, potentiostatic electrodeposition 250 seconds, so as to obtain Co0.67Al0.22(OH)2Cobalt aluminum complex hydroxide/hydrogen-oxygen
Change copper/foam copper tubular structure material.
Claims (3)
1. a kind of preparation method of hollow tubular structure electrode material, is comprised the following steps that：
A. pretreated copper-containing metal substrate is impregnated in sodium hydroxide and ammonium persulfate mixed solution, wherein sodium hydroxide
Concentration be 0.5-10.0mol/L, the concentration of ammonium persulfate is 0.05-1.00mol/L；Impregnate and taken out after 20-30min, spent
Ionized water is rinsed well, is placed in 30-80 DEG C of baking oven and is dried, that is, obtains grown the base of Kocide SD in copper-containing metal substrate
Bottom；The Kocide SD grown is nano bar-shape structure；Described copper-containing metal substrate is that foam copper, copper sheet, copper mesh or copper are closed
One of gold；
B. Kocide SD step A obtained/copper-containing metal substrate is as working electrode, and using Pt as to electrode, Ag/AgCl is ginseng
Than electrode, in mixed salt solution, potential is potentiostatic electrodeposition 150-400 seconds under the conditions of -0.9~-1.1V, is combined
Hydroxide/Kocide SD/copper-containing metal substrate tubular structure；
Mixed salt solution described in step B is the mixing salt solution of M salt and M ' salt composition, and wherein M is metal ion Ni2+Or
Co2+, M ' is metal ion Co2+、Al3+Or Fe3+, and M it is different from M ' when be Co2+；The anion of above two salt at least one
It is NO to plant3 -, another is NO3 -、Cl-Or SO4 2-；In mixed salt solution, the mol ratio of M salt and M ' salt is 1~4:1, total gold
Category ion concentration is 0.005-0.100mol/L；
Complex hydroxide described in step B is NixCo1-x(OH)2、NixAl2/3(1-x)(OH)2、CoxAl2/3(1-x)(OH)2、
NixFe2/3(1-x)(OH)2And CoxFe2/3(1-x)(OH)2Complex hydroxide, it is the structure of hollow tubular.
2. a kind of hollow tubular structure electrode material prepared according to the method described in claim 1, it is by being combined hydroxide
The hollow tubular structure material that thing/Kocide SD/copper-containing metal substrate is constituted.
3. hollow tubular structure electrode material according to claim 2, it is characterized in that the material microstructure is；Hydroxide
Copper nanorod growth is in copper-containing metal substrate, and complex hydroxide is grown in the hollow tube of Kocide SD nanometer rods outer wall formation
Shape structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510813390.9A CN105513831B (en) | 2015-11-23 | 2015-11-23 | A kind of hollow tubular structure electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510813390.9A CN105513831B (en) | 2015-11-23 | 2015-11-23 | A kind of hollow tubular structure electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105513831A CN105513831A (en) | 2016-04-20 |
| CN105513831B true CN105513831B (en) | 2017-10-20 |
Family
ID=55721734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510813390.9A Expired - Fee Related CN105513831B (en) | 2015-11-23 | 2015-11-23 | A kind of hollow tubular structure electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105513831B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105869908A (en) * | 2016-05-25 | 2016-08-17 | 东华大学 | Preparation method of core-shell Co3O4@Fe2O3 nanowire array |
| CN105938762A (en) * | 2016-07-12 | 2016-09-14 | 安徽大学 | Method for preparing flexible solid super capacitor based on linear Cu(OH)2@NiCo2O4 multilevel nano array |
| CN106226382B (en) * | 2016-08-08 | 2018-07-31 | 北京科技大学 | Nano porous copper/Cu (OH)2Nano-wire array sensor electrode material and preparation method thereof |
| CN107871627A (en) * | 2016-09-28 | 2018-04-03 | 南京大学 | Foam copper supports high capacitance flexible electrode material of CuO nanometer sheet and preparation method thereof |
| CN106517445B (en) * | 2016-12-07 | 2021-05-25 | 青岛海尔智能技术研发有限公司 | Preparation method and application of electroporation electrode structure |
| CN107879371B (en) * | 2017-11-17 | 2020-12-08 | 许昌学院 | Method for in-situ growth of needle-shaped copper hydroxide on surface of copper-based material |
| CN108109851A (en) * | 2017-12-20 | 2018-06-01 | 中国科学院深圳先进技术研究院 | A kind of preparation method of super capacitor, its electrode and its active material |
| CN108538609B (en) * | 2018-01-02 | 2019-10-18 | 北京化工大学 | A kind of iron Cu oxide/copper base electrode material and preparation method thereof |
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN108671923B (en) * | 2018-05-10 | 2021-06-29 | 宁波大学 | Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof |
| CN109055976B (en) * | 2018-08-03 | 2020-06-02 | 北京化工大学 | Transition metal nitride electrode material with multi-level structure and preparation method thereof |
| CN109811364B (en) * | 2019-01-10 | 2020-10-27 | 北京化工大学 | Ruthenium/cuprous oxide electro-catalytic material and preparation method thereof |
| CN109876846B (en) * | 2019-03-27 | 2022-01-25 | 浙江理工大学 | Three-dimensional self-supporting Cu3Preparation method of PNW @ CoFeP composite material |
| CN110223851A (en) * | 2019-05-23 | 2019-09-10 | 潍坊学院 | A kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material |
| CN110504107B (en) * | 2019-08-20 | 2020-10-16 | 吉林大学 | Nano composite electrode material, preparation method thereof and super capacitor |
| CN110890227B (en) * | 2019-12-10 | 2021-09-28 | 武汉理工大学 | Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof |
| CN110993362A (en) * | 2019-12-25 | 2020-04-10 | 湖北大学 | Novel three-dimensional electrode material, preparation method thereof and application thereof in super capacitor |
| CN111265705A (en) * | 2020-03-03 | 2020-06-12 | 北京科技大学 | Preparation method of antibacterial and antivirus copper-based filter screen |
| CN112542328B (en) * | 2020-12-02 | 2022-07-05 | 浙江大学 | Ternary layered metal hydroxide @ polyaniline composite electrode material and preparation method and application thereof |
| CN114530606B (en) * | 2022-01-06 | 2023-05-23 | 清华大学深圳国际研究生院 | Three-dimensional lithium-philic carbon interface modified copper-based current collector and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231435A (en) * | 2011-05-20 | 2011-11-02 | 合肥工业大学 | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate |
| CN104134788A (en) * | 2014-07-22 | 2014-11-05 | 南方科技大学 | Three dimensional gradient metal hydroxide/oxide electrode material and manufacture method and application thereof |
-
2015
- 2015-11-23 CN CN201510813390.9A patent/CN105513831B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231435A (en) * | 2011-05-20 | 2011-11-02 | 合肥工业大学 | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate |
| CN104134788A (en) * | 2014-07-22 | 2014-11-05 | 南方科技大学 | Three dimensional gradient metal hydroxide/oxide electrode material and manufacture method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Hierarchical NiAl Layered Double Hydroxide/Multiwalled Carbon Nanotube/Nickel Foam Electrodes with Excellent Pseudocapacitive Properties";Bo Wang,et al.;《ACS Applied Materials & Interfaces》;20140903;第6卷;第16304-16311页 * |
| "Three-dimensional NiFe layered double hydroxide film for high-efficiency oxygen evolution reaction";Zhiyi Lu,et al.;《Chem. Commun.》;20140325;第50卷;第6479-6482页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105513831A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105513831B (en) | A kind of hollow tubular structure electrode material and preparation method thereof | |
| CN108538609B (en) | A kind of iron Cu oxide/copper base electrode material and preparation method thereof | |
| Chen et al. | V2O3@ amorphous carbon as a cathode of zinc ion batteries with high stability and long cycling life | |
| CN103840145B (en) | A kind of preparation method of lithium-sulfur cell nano-tube array positive electrode | |
| CN108682561A (en) | A kind of electrode material for super capacitor and preparation method | |
| Zeng et al. | Electrodeposition of hierarchical manganese oxide on metal nanoparticles decorated nanoporous gold with enhanced supercapacitor performance | |
| CN102938331A (en) | Foam nickel-base MnO2/C composite electrode material and preparation method thereof | |
| CN102664107B (en) | Preparation method of nano-manganese dioxide electrode | |
| CN107403968A (en) | Aqoue seconary battery | |
| Zhou et al. | Tailored synthesis of nano-corals nickel-vanadium layered double hydroxide@ Co2NiO4 on nickel foam for a novel hybrid supercapacitor | |
| CN101113525A (en) | Pt-TiO2/Ti combination electrode and method for making same | |
| CN107256946A (en) | Battery | |
| Patil et al. | Template‐free synthesis of one‐dimensional cobalt sulfide nanorod array as an attractive architecture for overall water splitting | |
| CN107876071A (en) | Fe2P nano-array surface modification Ni (OH)2Liberation of hydrogen catalyst and its preparation method and application | |
| Ge et al. | Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction | |
| Chen et al. | High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower | |
| CN105789637B (en) | Area load has carbon nano pipe array electrode of Au nano particles and its preparation method and application | |
| Mondal et al. | Manganese oxide based hybrid nanofibers for supercapacitors | |
| CN108987123B (en) | Ternary composite super-capacitor electrode material and preparation method thereof | |
| Tan et al. | Zn–Co–S coatings with a rough and porous nano-dendrite structure for high-performance asymmetric supercapacitors without binder | |
| Xu et al. | Recent progress of self-supported air electrodes for flexible Zn-air batteries | |
| CN110723755B (en) | Fe7S8/α -FeOOH/iron-based electrode material and preparation method and application thereof | |
| CN106449141B (en) | Ti-alloy mesh substrate based on highly conductive ceramic watch facial mask prepares cobalt hydroxide/nickel electrode of super capacitor method | |
| CN106207203B (en) | A kind of nano-sheet Ni (OH)2Catalyst and its preparation method and application | |
| He et al. | Keggin-type polyoxometalate/thiospinel octahedron heterostructures for photoelectronic devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171020 Termination date: 20211123 |