CN111508717B - Novel three-dimensional silicon structure supercapacitor electrode material and preparation method thereof - Google Patents
Novel three-dimensional silicon structure supercapacitor electrode material and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 126
- 239000010703 silicon Substances 0.000 claims abstract description 126
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- 238000000034 method Methods 0.000 claims abstract description 41
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- 239000002070 nanowire Substances 0.000 claims description 40
- 238000004528 spin coating Methods 0.000 claims description 38
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 34
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- 238000000137 annealing Methods 0.000 claims description 23
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- 238000005507 spraying Methods 0.000 claims description 18
- 229920000767 polyaniline Polymers 0.000 claims description 17
- 239000002042 Silver nanowire Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- 235000012431 wafers Nutrition 0.000 description 49
- 238000005530 etching Methods 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 229910052709 silver Inorganic materials 0.000 description 16
- 239000004332 silver Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002131 composite material Substances 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
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- 239000002245 particle Substances 0.000 description 7
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 7
- 239000012047 saturated solution Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
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- 229910017709 Ni Co Inorganic materials 0.000 description 3
- 229910003267 Ni-Co Inorganic materials 0.000 description 3
- 229910003262 Ni‐Co Inorganic materials 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
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- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention provides a novel three-dimensional silicon structure supercapacitor electrode material and a preparation method thereof, wherein a three-dimensional silicon structure is used as a substrate, an active layer is prepared on the surface of the substrate, and a charge collection layer is covered on the surface of the active layer; the charge collection layer is prepared by taking a two-dimensional conductive material as a main body and a conductive polymer as a binder on the surface of the active layer, wherein the porous network-shaped charge collection layer with higher conductivity is prepared. When preparing electrode material with large area, in order to increase the collection efficiency of electric charge, metal gate electrode material is evaporated on the surface of the high conductive layer. The three-dimensional silicon structure electrode material prepared by the method does not need to consider the conductivity, purity and crystal form of the silicon substrate, and does not need to passivate the silicon surface, so that the raw material cost of the silicon electrode material is reduced, and the preparation method of the silicon electrode is simplified.
Description
Technical Field
The invention belongs to the field of electrode materials, and relates to a novel three-dimensional silicon structure supercapacitor electrode material and a preparation method thereof.
Background
The advent of innovative miniature portable devices, such as wireless microsensors or the widespread use of biomedical implanted micro-devices, has attracted considerable interest in the field of energy storage devices, from aeronautics to biomedicine. The specifications of such microdevices require high performance small size power supplies, including high power density and energy density, as well as long life and good compatibility with the microelectronics industry. Silicon, the second most abundant element on earth, is the best element studied in all chemical elements, and at the same time, most semiconductor elements are prepared from silicon, which is the most dominant element in the industries of photoelectron, microelectronics, etc. Therefore, the silicon is an ideal electrode material of the micro super capacitor for chip energy storage, and the micro super capacitor prepared by taking the silicon as the substrate can be well built into a chip together with a microelectronic circuit for power supply, so that the silicon has long-term application prospect.
The three-dimensional silicon structure has the advantages of small size and large specific surface area, is beneficial to carrying more electrode active substances, increases the contact area of electrode materials and electrolyte, and improves the specific capacity of devices. In the traditional silicon-based super capacitor, most of the silicon back electrode is used as a charge collection layer, for example, aluminum metal is evaporated on the back surface of monocrystalline silicon to be used as the charge collection layer, the structure needs to conduct charges through silicon, and the requirements on the purity and the conductivity of silicon are high in order to reduce the loss of the charges in the transmission process. High purity and high conductivity increase the cost of the raw material for silicon. At the same time, the surface of the silicon needs to be passivated or modified in order to prevent surface oxidation and photo-corrosion of the silicon. At present, based on the structure, researchers at home and abroad have prepared a series of silicon-based super capacitors, but the preparation steps are relatively complex, a CVD method, an ALD method or a high-temperature calcination method may be needed to passivate the surface of silicon in the preparation process, the process is relatively complex, and the manufacturing cost is relatively high.
Disclosure of Invention
The invention aims to provide a novel electrode material of a three-dimensional silicon structure super capacitor and a preparation method thereof.
The novel three-dimensional silicon structure supercapacitor electrode material is characterized in that silicon with a three-dimensional structure on the surface is used as a substrate, an active layer is arranged on the three-dimensional structure surface of a silicon substrate, and a porous network-shaped charge collection layer is arranged on the upper surface of the active layer.
Preferably, the surface of the charge collection layer is vapor-plated with a metal gate electrode material.
Preferably, the active layer material is a conductive polymer, a metal oxide and/or a metal hydroxide.
Preferably, the conductive polymer is polyaniline, polypyrrole or polythiophene, and the metal oxide is RuOX、WO3Or MnO of2Said metal hydroxides such as Ni (OH)2Or Co (OH)2。
Preferably, the charge collection layer is formed by coating a conductive polymer and a conductive two-dimensional material after being blended.
Preferably, the conductive polymer is PEDOT PSS; the two-dimensional conductive material is a carbon nano tube, a carbon nano wire or a metal nano wire; the metal nanowire is a silver nanowire or a copper-nickel alloy nanowire.
Preferably, the metal gate electrode material may be metal nickel, nano silver mesh.
The preparation method of the novel three-dimensional silicon structure supercapacitor electrode material is characterized by comprising the following steps:
and 3, evaporating metal gate electrode materials on the surface of the charge collection layer.
Preferably, the method for preparing the charge collection layer by the spin coating method in the step 2 comprises the following steps: and spin-coating 1-3 layers of PEDOT (Poly ethylene glycol Ether Co) doped with the two-dimensional conductive material on the active layer, wherein the PSS solution is annealed at 180 ℃ for 5-10 min for 100-90 s at the spin-coating time of 800-6000 rpm after one layer is spin-coated.
Preferably, the spraying method in step 2 is used for preparing the high-conductivity charge collection layer by: and spraying 1-3 layers of PEDOT (Poly ethylene glycol Ether-Co-Polymer) PSS solution doped with the two-dimensional conductive material on the active layer, wherein the spraying temperature is 80-250 ℃, the spraying time is 30-120 s, and after the spraying, annealing is carried out for 5-20 min at the annealing temperature of 100-250 ℃.
A supercapacitor made of the three-dimensional silicon structure supercapacitor electrode material.
The novel three-dimensional silicon structure supercapacitor electrode material is prepared by a method of solution spin coating or high-temperature spray coating, a porous network-shaped charge collection layer is prepared by doping two-dimensional conductive materials such as carbon nano tubes, carbon nano wires, metal nano wires and the like, the charge collection layer is moved upwards onto an active layer on the surface of a silicon substrate, the stability of the electrode material is determined by the active layer, and surface oxidation and corrosion of silicon in electroplating solution do not need to be considered. Without regard to the properties of the silicon substrate material, such as the purity and conductivity of the silicon substrate. The silicon substrate only plays a role of a support, so that the preparation can be carried out on any silicon substrate, in the practical application process, the preparation of the super capacitor can be carried out by utilizing the residual silicon raw materials of the semiconductor material, the preparation method is suitable for preparing the high-performance super capacitor on the silicon substrates with various specifications, even metallurgical-grade silicon wafers, and the cost is greatly reduced.
The structure is used as the electrode material of the super capacitor, has higher specific capacitance, lower equivalent internal resistance and good charge-discharge characteristic, and is compatible with the integrated circuit process.
And metal gate electrodes are continuously evaporated on the surface of the charge collection layer, so that an excellent transmission network can be provided for electrons and ions, the charge collection efficiency is improved, and the high-performance electrochemical energy storage of the super capacitor is realized.
Drawings
Fig. 1 (a) and (b) are respectively a structure of a conventional silicon-based supercapacitor electrode material and a structure diagram of a three-dimensional silicon-based supercapacitor electrode material provided by the present invention. Wherein 1 is a three-dimensional silicon structure substrate, 2 is an active layer, 3 is a charge collection layer, and 4 is a passivation layer.
Fig. 2 is PEDOT doped carbon nanotubes: SEM image of PSS solution.
FIG. 3 is a comparative graph of CV characteristic test curves of 4 electrode materials, examples 1, 2, 3, and 4, prepared by using a PSS solution as a charge collection layer and a carbon nanotube-doped PEDOT as a charge collection layer, and evaporating metal gate electrode materials, in which the conductive polymer PANI is used as an active layer, no charge collection layer is added, and pure PEDOT is spin-coated at a scanning speed of 50 mV/s.
FIG. 4 shows the concentration of the compound at 1mA/cm2Under the current density of charging and discharging, taking the conductive polymer PANI as an active layer, not adding a charge collection layer, spin-coating pure PEDOT, wherein PSS solution is used as the charge collection layer, PEDOT doped with carbon nano tubes is used as the charge collection layer, and additionally, 4 electrode materials prepared by evaporating metal gate electrode materials are added, namely GCD comparison graphs of examples 1, 2, 3 and 4.
Fig. 5 shows the EIS spectrum of example 6, which is an electrode material prepared by using a metal hydroxide as an active layer, PEDOT doped with silver nanowires as a charge collection layer, and evaporating a metal silver gate electrode.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Selecting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm, cutting the silicon wafer into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) And spin-coating 3 layers of PEDOT on the silicon nanowire, namely, pre-treating PSS solution to improve the conductivity and the adhesion so as to facilitate the subsequent electrochemical deposition, and annealing for 5min at 180 ℃ after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparing a conductive polymer polyaniline active layer by an electrochemical deposition method:
and (3) taking the silicon substrate in the step (2) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, preparing a polyaniline active layer by adopting a traditional three-electrode system, wherein the concentration of an aniline monomer is 0.3mol/L, the voltage is 2V, and the polyaniline is prepared by performing electrochemical deposition in a 1mol/L dilute hydrochloric acid solution by a constant voltage method for 10 min.
Example 2
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Selecting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm, cutting the silicon wafer into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) And spin-coating 3 layers of PEDOT on the silicon nanowire, namely, pre-treating PSS solution to improve the conductivity and the adhesion so as to facilitate the subsequent electrochemical deposition, and annealing for 5min at 180 ℃ after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparing a conductive polymer polyaniline active layer by an electrochemical deposition method:
and (3) taking the silicon substrate in the step (2) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, preparing a polyaniline active layer by adopting a traditional three-electrode system, wherein the concentration of an aniline monomer is 0.3mol/L, the voltage is 2V, electrochemical deposition of polyaniline is carried out in a 1mol/L dilute hydrochloric acid solution by a constant voltage method, and the electroplating time is 10 min.
(4) Solution spin coating method preparation of pure PEDOT: PSS charge collection layer:
spin-coating 3 layers of pure PEDOT on the silicon substrate in the step (3): PSS solution, spin speed 2000rpm, time 30 s. And annealing at 180 ℃ for 5min after each layer is spun, and annealing at 180 ℃ for 20min for the final composite electrode.
Example 3
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Cutting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) And spin-coating 3 layers of PEDOT on the silicon nanowire, namely, pre-treating PSS solution to improve the conductivity and the adhesion so as to facilitate the subsequent electrochemical deposition, and annealing for 5min at 180 ℃ after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparing a conductive polymer polyaniline active layer by an electrochemical deposition method:
preparing polyaniline by taking the silicon substrate in the step (2) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode through a traditional three-electrode system, wherein the concentration of an aniline monomer is 0.3mol/L, the voltage is 2V, and the polyaniline is prepared by performing electrochemical deposition in a 1mol/L dilute hydrochloric acid solution by a constant voltage method for 10 min;
(4) preparing PEDOT doped with silver nanowires by a solution spin-coating method: PSS charge collection layer:
spin-coating 3 layers of PEDOT on the silicon substrate in the step (3): a mixed solution of PSS and silver nanowires, wherein the ratio PEDOT: the volume of the PSS solution is 2 times of that of the silver nanowire (isopropanol) solution, the concentration of the silver nanowires is 5mg/ml, the spin-coating speed is 2000rpm, and the time is 30 s. And annealing at 180 ℃ for 5min after each layer is spun, and annealing at 180 ℃ for 20min for the final composite electrode.
Example 4
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Selecting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm, cutting the silicon wafer into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) And spin-coating 3 layers of PEDOT on the silicon nanowire, namely, pre-treating PSS solution to improve the conductivity and the adhesion so as to facilitate the subsequent electrochemical deposition, and annealing for 5min at 180 ℃ after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparing a conductive polymer polyaniline active layer by an electrochemical deposition method:
preparing polyaniline by taking the silicon substrate in the step (2) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode through a traditional three-electrode system, wherein the concentration of an aniline monomer is 0.3mol/L, the voltage is 2V, and the polyaniline is prepared by performing electrochemical deposition in a 1mol/L dilute hydrochloric acid solution by a constant voltage method for 10 min;
(3) preparing PEDOT doped with silver nanowires by a solution spin-coating method: PSS charge collection layer
Spin-coating 3 layers of PEDOT on the silicon substrate in the step (2): a mixed solution of PSS and silver nanowires, wherein the ratio PEDOT: the volume of the PSS solution is 2 times of that of the isopropanol solution of the silver nanowires, the concentration of the silver nanowires is 5mg/ml, the spin-coating speed is 2000rpm, and the time is 30 s. And annealing at 180 ℃ for 5min after each layer is spun, and annealing at 180 ℃ for 20min for the final composite electrode.
(4) And depositing a metal silver gate electrode on the surface of the charge collection layer by evaporation, wherein the thickness of the metal silver gate electrode is less than 4 mu m.
Example 5
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Selecting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm, cutting the silicon wafer into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) And spin-coating 3 layers of PEDOT on the silicon nanowire, namely, pre-treating PSS solution to improve the conductivity and the adhesion so as to facilitate the subsequent electrochemical deposition, and annealing for 5min at 180 ℃ after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparing a Ni-Co metal hydroxide active layer by an electrochemical deposition method:
taking the silicon substrate in the step (2) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, and preparing Ni (OH) by adopting a traditional three-electrode system2And Co (OH)2The active layer of (1). And performing electrochemical deposition in electroplating solution (mixed solution of nickel sulfate and cobalt nitrate) at constant voltage of 4V to obtain active layer, wherein the concentration of nickel sulfate is 5mmol/L, the concentration of cobalt nitrate is 5mmol/L, and the electroplating time is 20 min.
(4) Preparing PEDOT doped with silver nanowires by a solution spin-coating method: PSS charge collection layer:
spin-coating 3 layers of PEDOT on the silicon substrate in the step (3): a mixed solution of PSS and silver nanowires; wherein, PEDOT: the volume of the PSS solution is 2 times of that of the isopropanol solution of the silver nanowires, the concentration of the silver nanowires is 5mg/ml, the spin-coating speed is 2000rpm, and the time is 30 s. And annealing at 180 ℃ for 5min after each layer is spun, and annealing at 180 ℃ for 20min for the final composite electrode.
(5) And depositing a metal silver gate electrode on the surface of the charge collection layer by evaporation, wherein the thickness of the metal silver gate electrode is less than 4 mu m.
Example 6
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Selecting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm, cutting the silicon wafer into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) Spin-coating 3 layers of PEDOT on a silicon nanowire, namely, pre-treating a PSS solution, and annealing at 180 ℃ for 5min after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparation of Ni-Co metal hydroxide active layer by electrochemical deposition method
Taking the silicon substrate in the step (1) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, and preparing Ni (OH) by adopting a traditional three-electrode system2And Co (OH)2The active layer of (1). And performing electrochemical deposition in electroplating solution (mixed solution of nickel sulfate and cobalt nitrate) at constant voltage of 4V to obtain active layer, wherein the concentration of nickel sulfate is 5mmol/L, the concentration of cobalt nitrate is 5mmol/L, and the electroplating time is 20 min.
(4) Preparation of PEDOT by solution spray: PSS charge collection layer
Spraying 3 layers of PEDOT on the silicon substrate in the step (3): and spraying the PSS solution for 60s at 120 ℃, and annealing at the annealing temperature of 180 ℃ for 20min after spraying.
(5) And depositing a metal silver gate electrode on the surface of the charge collection layer by evaporation, wherein the thickness of the metal silver gate electrode is less than 4 mu m.
Example 7
(1) And etching by a solution method to prepare silicon nanowires (SiNWs), and carrying out secondary treatment on the silicon nanowires to prepare the silicon substrate with the surface in a three-dimensional structure.
(a) Selecting an N-type (100 crystal orientation) single-side polished silicon wafer with the resistivity of 5-7 omega cm, cutting the silicon wafer into 1 cm-2 cm sample wafers, and washing the sample wafers for multiple times by using ethanol and deionized water; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon chip into chlorobenzene saturated solution of phosphorus pentachloride for secondary treatment, wherein the treatment time is 3h and the treatment temperature is 120 ℃.
(2) And spin-coating 3 layers of PEDOT on the silicon nanowire, namely, pre-treating PSS solution to improve the conductivity and the adhesion so as to facilitate the subsequent electrochemical deposition, and annealing for 5min at 180 ℃ after each layer is spin-coated. The spin coating time was 30s and the rotation speed was 2000 rpm.
(3) Preparing a Ni-Co metal hydroxide active layer by an electrochemical deposition method:
taking the silicon substrate in the step (2) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, and preparing Ni (OH) by adopting a traditional three-electrode system2And Co (OH)2The active layer of (1). And performing electrochemical deposition in electroplating solution (mixed solution of nickel sulfate and cobalt nitrate) at constant voltage of 4V to obtain active layer, wherein the concentration of nickel sulfate is 5mmol/L, the concentration of cobalt nitrate is 5mmol/L, and the electroplating time is 20 min.
(4) Preparing PEDOT doped with carbon nanotubes by a solution spin-coating method: PSS charge collection layer:
spin-coating 3 layers of PEDOT on the silicon substrate in the step (3): the mixed solution of PSS and carbon nanotubes, as shown in fig. 2, shows that the carbon nanotubes are uniformly dispersed in the PEDOT: PSS solution; wherein, PEDOT: the volume of the PSS solution is 2 times of that of the carbon nanotube solution, the concentration of the carbon nanotubes is 6mg/ml, the spin-coating speed is 2000rpm, and the time is 30 s. And annealing at 180 ℃ for 5min after each layer is spun, and annealing at 180 ℃ for 20min for the final composite electrode.
(5) And depositing a metal silver gate electrode on the surface of the charge collection layer by evaporation, wherein the thickness of the metal silver gate electrode is less than 4 mu m.
The prepared novel three-dimensional silicon structure super capacitor electrode material is used as a working electrode, and a platinum sheet is used as a counter electrodeAn Ag/AgCl electrode is used as a reference electrode, electrochemical tests are carried out in 1mol/L sodium sulfate electrolyte, and the electrochemical performance of the composite electrode is detected, and the results are shown in fig. 3, fig. 4 and fig. 5. Wherein FIG. 3 is a graph comparing CV curves at a scan rate of 50mV/s for examples 1, 2, 3, 4. FIG. 4 shows the composite electrodes of examples 1, 2, 3 and 4 at 1mA/cm2The GCD curve comparison graphs of the charge and discharge current density and the graphs in figures 3 and 4 show that the conductive polymer PANI introduced by electroplating has a significantly smaller specific capacitance without a charge collection layer than that with pure PEDOT: PSS as the charge collection layer, which shows that the high-conductivity charge collection layer can improve the ion transmission capability, and after the metal nanowire is introduced, the discharge time of the composite electrode material is prolonged, the impedance is also small, which shows that the introduction of the metal nanowire can improve the conductivity and the stability of the electrode material. And metal gate electrodes are continuously evaporated on the surface of the charge collection layer, so that a more excellent channel is provided for charge and ion transmission, and the charge collection efficiency is improved. Therefore, the novel three-dimensional silicon structure composite electrode material prepared by the method has excellent electrochemical performance and can be applied to electrode materials of silicon micro super capacitors.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. The three-dimensional silicon structure supercapacitor electrode material is characterized in that silicon with a three-dimensional structure on the surface is used as a substrate, an active layer is arranged on the three-dimensional structure surface of a silicon substrate, and a porous network-shaped charge collection layer is arranged on the upper surface of the active layer;
the charge collection layer is formed by blending and coating a conductive polymer and a conductive two-dimensional material, and a metal gate electrode material is evaporated on the surface of the charge collection layer; the charge-collection layer is moved up to an active layer on the surface of the silicon substrate, and the stability of the metal gate electrode material is determined by the active layer.
2. According to claim1, the electrode material of the three-dimensional silicon structure super capacitor is characterized in that the active layer substance is a conductive polymer, a metal oxide and/or a metal hydroxide; the conductive polymer is polyaniline, polypyrrole or polythiophene, and the metal oxide is RuOX、WO3Or MnO2Said metal hydroxide Ni (OH)2Or Co (OH)2。
3. The electrode material of the supercapacitor with the three-dimensional silicon structure according to claim 1, wherein the conductive polymer of the charge collection layer is PEDOT PSS; the conductive two-dimensional material is a carbon nano tube, a carbon nano wire or a metal nano wire; the metal nanowire is a silver nanowire or a copper-nickel alloy nanowire.
4. The three-dimensional silicon structure supercapacitor electrode material according to claim 1, wherein the metal gate electrode material is a metal nickel or nano silver mesh.
5. The preparation method of the electrode material of the three-dimensional silicon structure supercapacitor according to any one of claims 1 to 4, comprising the following steps:
step 1, taking a three-dimensional silicon structure as a substrate, and preparing an active layer on the surface of the three-dimensional structure of the silicon substrate by a solution method, a soaking method, a spraying method or an electrochemical deposition method;
step 2, blending the conductive polymer and the conductive two-dimensional material to prepare a uniform and stable solution, and covering the uniform and stable solution on the active layer substrate by adopting a spin coating or spraying mode to prepare a porous network-shaped charge collection layer;
and 3, evaporating metal gate electrode materials on the surface of the charge collection layer.
6. The method of claim 5, wherein the step 2 of preparing the charge-collecting layer by spin coating comprises: and spin-coating 1-3 layers of PEDOT (Poly ethylene glycol Ether Co) doped with the two-dimensional conductive material on the active layer, wherein the PSS solution is annealed at 180 ℃ for 5-10 min for 100-90 s at the spin-coating time of 800-6000 rpm after one layer is spin-coated.
7. The method of claim 5, wherein the step 2 of spraying to form the highly conductive charge-collecting layer comprises: and spraying 1-3 layers of PEDOT (Poly ethylene glycol Ether-Co-Polymer) PSS solution doped with the two-dimensional conductive material on the active layer, wherein the spraying temperature is 80-250 ℃, the spraying time is 30-120 s, and after the spraying, annealing is carried out for 5-20 min at the annealing temperature of 100-250 ℃.
8. A supercapacitor made of the three-dimensional silicon structure supercapacitor electrode material according to any one of claims 1 to 4.
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