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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- copper
- kocide
- tubular structure
- hollow tubular
- complex hydroxide
- 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.)
- Granted
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 239000002073 nanorod Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 238000009472 formulation Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 75
- 229910052802 copper Inorganic materials 0.000 claims description 73
- 239000010949 copper Substances 0.000 claims description 73
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 67
- 239000006260 foam Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 4
- 239000002070 nanowire Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 abstract 5
- 239000005750 Copper hydroxide Substances 0.000 abstract 5
- 229910001956 copper hydroxide Inorganic materials 0.000 abstract 5
- 239000002131 composite material Substances 0.000 abstract 4
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000004626 scanning electron microscopy Methods 0.000 description 10
- 208000036695 Syndromic diarrhea Diseases 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 208000007004 trichohepatoenteric syndrome Diseases 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229910000863 Ferronickel Inorganic materials 0.000 description 4
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000010351 charge transfer process Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910016719 Ni0.5Co0.5(OH)2 Inorganic materials 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- YYCNOHYMCOXPPJ-UHFFFAOYSA-N alumane;nickel Chemical compound [AlH3].[Ni] YYCNOHYMCOXPPJ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Manufacturing & Machinery (AREA)
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.
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 true CN105513831A (en) | 2016-04-20 |
CN105513831B 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) |
Cited By (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 |
CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
CN106517445A (en) * | 2016-12-07 | 2017-03-22 | 青岛海尔智能技术研发有限公司 | Preparation method for electroporation electrode structure and application |
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 |
CN107879371A (en) * | 2017-11-17 | 2018-04-06 | 许昌学院 | A kind of method in copper-based material surface in situ growth needle-like Kocide SD |
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 |
CN108538609A (en) * | 2018-01-02 | 2018-09-14 | 北京化工大学 | A kind of iron Cu oxide/copper base electrode material and preparation method thereof |
CN108671923A (en) * | 2018-05-10 | 2018-10-19 | 宁波大学 | Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water |
CN109055976A (en) * | 2018-08-03 | 2018-12-21 | 北京化工大学 | A kind of multilevel structure transition metal nitride electrode material and preparation method thereof |
CN109811364A (en) * | 2019-01-10 | 2019-05-28 | 北京化工大学 | A kind of ruthenium/cuprous oxide electrocatalysis material and preparation method thereof |
CN109876846A (en) * | 2019-03-27 | 2019-06-14 | 浙江理工大学 | A kind of Cu of three-dimensional self-supporting3The preparation 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 |
CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
CN110504107A (en) * | 2019-08-20 | 2019-11-26 | 吉林大学 | A kind of nanometer combined electrode material and preparation method thereof and supercapacitor |
CN110890227A (en) * | 2019-12-10 | 2020-03-17 | 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 |
CN112542328A (en) * | 2020-12-02 | 2021-03-23 | 浙江大学 | Ternary layered metal hydroxide @ polyaniline composite electrode material and preparation method and application thereof |
CN114530606A (en) * | 2022-01-06 | 2022-05-24 | 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 |
---|
BO WANG,ET AL.: ""Hierarchical NiAl Layered Double Hydroxide/Multiwalled Carbon Nanotube/Nickel Foam Electrodes with Excellent Pseudocapacitive Properties"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
ZHIYI LU,ET AL.: ""Three-dimensional NiFe layered double hydroxide film for high-efficiency oxygen evolution reaction"", 《CHEM. COMMUN.》 * |
Cited By (28)
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 |
CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 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 |
CN106517445A (en) * | 2016-12-07 | 2017-03-22 | 青岛海尔智能技术研发有限公司 | Preparation method for electroporation electrode structure and application |
CN107879371A (en) * | 2017-11-17 | 2018-04-06 | 许昌学院 | A kind of method in copper-based material surface in situ growth needle-like Kocide SD |
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 |
CN108538609A (en) * | 2018-01-02 | 2018-09-14 | 北京化工大学 | A kind of iron Cu oxide/copper base electrode material and preparation method thereof |
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 |
CN108671923A (en) * | 2018-05-10 | 2018-10-19 | 宁波大学 | Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water |
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 |
CN109055976A (en) * | 2018-08-03 | 2018-12-21 | 北京化工大学 | A kind of multilevel structure transition metal nitride electrode material and preparation method thereof |
CN109811364A (en) * | 2019-01-10 | 2019-05-28 | 北京化工大学 | A kind of ruthenium/cuprous oxide electrocatalysis material and preparation method thereof |
CN109876846A (en) * | 2019-03-27 | 2019-06-14 | 浙江理工大学 | A kind of Cu of three-dimensional self-supporting3The preparation method of PNW@CoFeP composite material |
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 |
CN110504107A (en) * | 2019-08-20 | 2019-11-26 | 吉林大学 | A kind of nanometer combined electrode material and preparation method thereof and supercapacitor |
CN110504107B (en) * | 2019-08-20 | 2020-10-16 | 吉林大学 | Nano composite electrode material, preparation method thereof and super capacitor |
CN110890227A (en) * | 2019-12-10 | 2020-03-17 | 武汉理工大学 | Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof |
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 |
CN112542328A (en) * | 2020-12-02 | 2021-03-23 | 浙江大学 | Ternary layered metal hydroxide @ polyaniline composite electrode material and preparation method and application thereof |
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 |
CN114530606A (en) * | 2022-01-06 | 2022-05-24 | 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 |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN105513831B (en) | 2017-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105513831B (en) | A kind of hollow tubular structure electrode material and preparation method thereof | |
Guo et al. | Non-noble metal-transition metal oxide materials for electrochemical energy storage | |
Lo et al. | Synthesis of Ni (OH) 2 nanoflakes on ZnO nanowires by pulse electrodeposition for high-performance supercapacitors | |
CN108538609B (en) | A kind of iron Cu oxide/copper base electrode material and preparation method thereof | |
CN102709058B (en) | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors | |
Zeng et al. | Electrodeposition of hierarchical manganese oxide on metal nanoparticles decorated nanoporous gold with enhanced supercapacitor performance | |
Liu et al. | Three-dimensional interconnected cobalt sulfide foam: Controllable synthesis and application in supercapacitor | |
CN105280394A (en) | Multilayer structure-based novel battery type supercapacitor with high power density and high energy density and preparation method | |
CN102664107B (en) | Preparation method of nano-manganese dioxide electrode | |
CN102938331A (en) | Foam nickel-base MnO2/C composite electrode material and preparation method thereof | |
JP5022567B2 (en) | Electrochemical cell | |
CN108899222B (en) | Preparation method of supercapacitor electrode material | |
Deng et al. | Self-supported Ni3S2/NiCo2O4 core-shell flakes-arrays on Ni foam for enhanced charge storage properties | |
JP2006510172A5 (en) | ||
Gao et al. | Core-shell Cu2-xS@ CoS2 heterogeneous nanowire array with superior electrochemical performance for supercapacitor application | |
CN109786135A (en) | A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof | |
CN107768150A (en) | Copper ion doped polyaniline electrode with carbon cloth as substrate and preparation method thereof | |
CN109950062A (en) | Nickel foam load α-Co (OH) in situ2/α-Ni(OH)2Hetero-junctions nanometer rods and preparation method and application | |
Li et al. | Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material | |
CN105789637B (en) | Area load has carbon nano pipe array electrode of Au nano particles and its preparation method and application | |
CN104867680A (en) | NiCo2O4@NiCo2O4 nanometer material for super capacitor electrode and preparation method thereof | |
CN102709060A (en) | High-performance nickel-cobalt oxide composite nanowire film for super capacitor | |
CN108987123A (en) | A kind of manganese dioxide-expanded graphite-cotton fiber tri compound electrochemical capacitance electrode material and preparation method thereof | |
CN110723755B (en) | Fe7S8/α -FeOOH/iron-based electrode material and preparation method and application thereof | |
CN116759584A (en) | Ultrahigh specific surface area current collector with oxide/carbon composite deposited on surface and preparation method and application thereof |
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 |
Granted publication date: 20171020 Termination date: 20211123 |
|
CF01 | Termination of patent right due to non-payment of annual fee |