CN112331492A - Preparation method of self-supporting porous silicon/ZnO composite material - Google Patents
Preparation method of self-supporting porous silicon/ZnO composite material Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- YAAXAGKSQIWLQT-UHFFFAOYSA-H [Si+4].C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound [Si+4].C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] YAAXAGKSQIWLQT-UHFFFAOYSA-H 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- BVDPFTQTMQKPGQ-UHFFFAOYSA-N ethanol hydrofluoride Chemical compound F.CCO BVDPFTQTMQKPGQ-UHFFFAOYSA-N 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 56
- 239000011787 zinc oxide Substances 0.000 abstract description 28
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000002161 passivation Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- H01G11/84—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
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/46—Metal oxides
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a self-supporting porous silicon/ZnO composite material, which comprises the following preparation steps: preparing self-supporting porous silicon by adopting multi-step anodic oxidation corrosion of p-type monocrystalline silicon; growing ZnO seed crystals, dispersing zinc oxide solution between the porous silicon layers by utilizing vacuum suction filtration, and growing the ZnO seed crystals in an argon atmosphere; preparing the composite material, namely promoting the growth of zinc oxide seed crystals between porous silicon layers into a nano zinc oxide layer by a hydrothermal synthesis method to form the micro-nano porous silicon/ZnO composite material. The invention realizes the growth and the stripping of the porous silicon slice layer by a monocrystalline silicon multi-step anodic oxidation corrosion method; the passivation of the surface of the porous silicon is realized through the nano zinc oxide layer on the surface of the porous silicon, the high resistance and the high reaction activity of the surface of the porous silicon are improved, the capacitance characteristic and the electrochemical stability of the porous silicon are greatly improved, and the application prospect of the porous silicon in the field of supercapacitors is widened.
Description
Technical Field
The invention belongs to the field of electrode materials, and relates to a preparation method of a self-supporting porous silicon/ZnO composite material.
Background
With the development of scientific technology, people can not leave electronic equipment in life, work and travel, and the demand of the future society for the super capacitor can be expected to show the increase of power function. Supercapacitors, also called electrochemical capacitors, have a high power density and a long cycle life, and activated carbon is now common as electrode material for supercapacitors. Porous silicon has a porous structure similar to activated carbon, has an ultra-high specific surface area, and has been reported to be applied to capacitors. Meanwhile, the preparation of the porous silicon is simple, the cost is low, and the industrialization is easy to realize, but the application of the porous silicon in the super capacitor is hindered due to the high resistance and the high reactivity. Therefore, the high resistance and the high reactivity of the silicon are reduced by scientific means, which has important and profound significance for developing the application of the porous silicon in the field of the super capacitor.
At present, the main scientific means is to wrap a pseudo-capacitance layer on the porous surface to realize passivation of porous silicon and reduce the electrochemical characteristics of the porous surface, but common electrode materials of the super capacitor with the pseudo-capacitance layer comprise ruthenium oxide, yttrium oxide, manganese oxide and the like, the process is complex, the cost is high, and the application of the super capacitor is limited. Therefore, the search for a method which has simple process and low cost and can realize passivation of the surface of the porous silicon and improve the capacitance characteristic of the porous silicon becomes the focus of the current technology.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting porous silicon/ZnO composite material, which forms the porous silicon/ZnO composite material with a nano zinc oxide layer wrapping the surface of a porous silicon by a monocrystalline silicon multistep anodic oxidation corrosion method and a zinc oxide hydrothermal synthesis method, and achieves multiple effects of passivating the surface of the porous silicon and improving the light-emitting characteristic and the capacitance characteristic of the porous silicon. The preparation method is simple in preparation process, environment-friendly, low in cost and convenient for realizing industrial application.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a self-supporting porous silicon/ZnO composite material comprises the following steps:
step 1, preparing self-supporting porous silicon, namely fixing p-type monocrystalline silicon subjected to ultrasonic cleaning by acetone into an electrolytic tank, enabling the unpolished side of the p-type monocrystalline silicon to be in complete contact with the bottom of an etching tank and a cathode electrode, enabling the polished side of the p-type monocrystalline silicon to be in contact with an etching solution, alternately etching a monocrystalline silicon wafer step by step, taking out the porous silicon after etching, and repeatedly washing the porous silicon with ionized water to remove electrolyte residues on the surface of the porous silicon;
step 2, growing ZnO seed crystals, putting the porous silicon treated in the step 1 into a silicon zinc acetate solution, performing vacuum filtration, and performing high-temperature heat preservation in an argon atmosphere;
and 3, preparing the composite material, namely putting the non-hydrolytic water-soluble zinc salt, weak base and water into a beaker, uniformly stirring, putting the porous silicon treated in the step 2 into the beaker, transferring the porous silicon into a reaction kettle, putting the reaction kettle into an incubator, and carrying out heat preservation for 5-10h at 90 ℃.
Further, the etching solution in the step 1 is hydrofluoric acid (HF) ethanol solution, and the volume ratio of hydrofluoric acid to absolute ethyl alcohol is 1: 1.
further, in the step 1, the growth and the peeling of the porous silicon wafer layer are realized by alternately controlling the current density and the corrosion time, and the current density is 30mA/cm alternately in steps2、80mA/cm2And the etching time is 30min and 1 min.
Furthermore, in the step 2, zinc acetate dihydrate and absolute ethyl alcohol can be selected for preparing the zinc acetate solution, and the concentration can be 0.08-0.16 mol/L.
Further, in step 2, the temperature of the high temperature heat preservation is controlled at 380 ℃ of 340-.
Further, in the step 2, the high-temperature heat preservation time is controlled to be 20-40 min.
Further, in step 3, the non-hydrolyzable water-soluble zinc salt is nitrate or sulfate.
Further, in step 3, the weak base is ammonia or urea.
Further, in the step 3, after the non-hydrolytic water-soluble zinc salt, the weak base and the water are stirred and mixed evenly, the pH value of the solution is controlled between 10 and 11.
The invention has the beneficial effects that:
the invention obtains the self-supporting porous silicon/ZnO composite material by combining a multi-step anodic oxidation corrosion method and a zinc oxide hydrothermal synthesis method. Firstly, obtaining self-supporting porous silicon by a multi-step anodic oxidation corrosion method of p-type monocrystalline silicon, realizing the stripping and growth of the porous silicon, forming the self-supporting porous silicon, improving the energy density on the surface of the porous silicon, then leading a silicon zinc acetate solution to fully enter between porous silicon layers by vacuum filtration to form a solution film, forming a ZnO seed crystal layer by pyrolysis under the argon atmosphere, finally realizing the growth of a nano zinc oxide layer by hydrothermally synthesizing zinc oxide particles by zinc salt and weak base, specifically, the nano zinc oxide layer is positioned between the porous silicon layers, and wraps the multi-layer silicon surface, thereby realizing passivation on the porous silicon surface, improving the high resistance and the high reaction activity of the porous silicon surface, and the synergistic effect of the pseudocapacitance characteristic of the zinc oxide and the double electric layer characteristic of the porous silicon is utilized to greatly improve the capacitance characteristic and the electrochemical stability of the porous silicon and widen the application prospect of the porous silicon in the field of supercapacitors. The preparation method is simple in preparation process, environment-friendly, low in cost and convenient for realizing industrial application.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a self-supporting porous silicon/ZnO composite material comprises the following steps:
material selection
A p-type monocrystalline silicon wafer with resistivity of 0.01-0.04 omega cm, and polishing one side.
Step 1: preparing self-supporting porous silicon: putting a p-type monocrystalline silicon wafer with the resistivity of 0.01-0.04 omega-cm into acetone, ultrasonically cleaning for 5-8min to remove impurities on the surface of the silicon, and cutting the treated monocrystalline silicon wafer into squares of 20mm multiplied by 20 mm; fixing the treated p-type single crystal silicon in an electrolytic bathOne side of the polished silicon wafer is completely contacted with the bottom of the corrosion groove and the cathode electrode, one side of the polished silicon wafer is contacted with a corrosive liquid, the monocrystalline silicon wafer is corroded step by step alternately, a hydrofluoric acid (HF) ethanol solution is selected as an electrolyte, and the volume ratio of the hydrofluoric acid to the absolute ethanol is 1: 1; step-by-step alternating current density of 30mA/cm2、80mA/cm2The etching time is 30min and 1min, and the growth and the stripping of the porous silicon wafer layer are realized; and taking out the porous silicon after corrosion, and repeatedly washing the porous silicon with ionized water to remove electrolyte residues on the surface.
Step 2: growing ZnO seed crystal: 99.5 percent of zinc acetate dihydrate is selected as a provider of main zinc for growing ZnO seed crystal, and absolute ethyl alcohol is used as a solvent. In the preparation process, 0.06mol of zinc acetate dihydrate is weighed, 0.4L of absolute ethyl alcohol is poured into a beaker, the weighed zinc acetate dihydrate is slowly added under the condition of stirring, after the zinc acetate dihydrate is completely dissolved, the porous silicon sample treated in the step 1 is soaked in the solution, and the solution is filtered in vacuum equipment, so that the zinc acetate silicate solution fully enters between the porous silicon layers, and a solution film is formed between the porous silicon layers. And then placing the sample in an argon atmosphere, and preserving the temperature for 35min at 360 ℃.
And step 3: preparing a composite material: weighing 0.002mol of zinc nitrate hexahydrate, putting into 80ml of water, dripping ammonia water, stirring uniformly, controlling the pH of the solution to be between 10 and 11, putting the porous silicon treated in the step 2, transferring to a reaction kettle, putting into a heat preservation box, and preserving heat for 8 hours at 90 ℃.
Example 2
A preparation method of a self-supporting porous silicon material comprises the following steps:
material selection
Preparation of self-supporting porous silicon: putting a p-type monocrystalline silicon wafer with the resistivity of 0.01-0.04 omega-cm into acetone, ultrasonically cleaning for 5-8min to remove impurities on the surface of the silicon, and cutting the treated monocrystalline silicon wafer into squares of 20mm multiplied by 20 mm; fixing the processed p-type monocrystalline silicon in an electrolytic tank, enabling the unpolished side of the p-type monocrystalline silicon to be in complete contact with the bottom of an etching tank and a cathode electrode, enabling the polished side of the p-type monocrystalline silicon to be in contact with an etching solution, etching the monocrystalline silicon by steps alternately, selecting a hydrofluoric acid (HF) ethanol solution as an electrolyte, and enabling the volume ratio of the hydrofluoric acid to the absolute ethyl alcohol to be 1: 1; is divided intoStep-alternating current density of 30mA/cm2、80mA/cm2The etching time is 30min and 1min, and the growth and the stripping of the porous silicon wafer layer are realized; and taking out the porous silicon after corrosion, and repeatedly washing the porous silicon with ionized water to remove electrolyte residues on the surface.
The samples of the above-mentioned examples 1 to 2 were subjected to electrochemical test tests. Firstly, TiW alloy with the thickness of 150nm growing on the back of the sample of the embodiment 1-2 is used as a current collector to collect electrons by a magnetron sputtering method, and a copper wire is led out by conductive silver paste to prepare an electrochemical test sample. During testing, the working electrode is the sample of embodiment 1-2, the reference electrode is Ag/AgCl, the auxiliary electrode is platinum, the electrolyte is 1mol/LKCl solution, the cyclic voltammetry scanning voltage interval is-0.5-0.5V, the scanning rate is 5mV/s, the constant current charging and discharging current is 5mA, and the test results are as follows.
Table 1 shows the oxidation peaks (peak Epa and peak Ipa) and the reduction peaks (peak Epc and peak Ipc) of the cyclic voltammograms of the samples of example 1-2, as follows, it can be seen that the cyclic voltammograms of the self-supporting porous silicon have no oxidation peaks and reduction peaks, and have a small specific capacity, and the oxidation peaks and reduction peaks occur due to the addition of zinc oxide.
| Epa(V) | Ipa(A) | Epc(V) | Ipc(A) | |
| Example 1 | 0.033 | -1.039 | 0.216 | 1.317 |
| Example 2 | Is free of | Is free of | Is free of | Is free of |
Table 1 examples 1-2 oxidation peak, reduction peak data for cyclic voltammograms of samples
Table 2 shows the charge and discharge characteristic data of the samples of the embodiment 1-2, it can be known that the self-supporting porous silicon/ZnO composite material has a much longer discharge time than the self-supporting porous silicon, and the calculated specific capacity of the electrode is much larger, which is nearly increased by 100 times.
Table 2 charge and discharge characteristic data of samples of embodiment examples 1-2
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims.
Claims (9)
1. A preparation method of a self-supporting porous silicon/ZnO composite material is characterized by comprising the following preparation steps:
step 1, preparing self-supporting porous silicon, namely fixing p-type monocrystalline silicon subjected to ultrasonic cleaning by acetone into an electrolytic tank, enabling the unpolished side of the p-type monocrystalline silicon to be in complete contact with the bottom of an etching tank and a cathode electrode, enabling the polished side of the p-type monocrystalline silicon to be in contact with an etching solution, alternately etching a monocrystalline silicon wafer step by step, taking out the porous silicon after etching, and repeatedly washing the porous silicon with ionized water to remove electrolyte residues on the surface of the porous silicon;
step 2, growing ZnO seed crystals, putting the porous silicon treated in the step 1 into a silicon zinc acetate solution, performing vacuum filtration, and performing high-temperature heat preservation in an argon atmosphere;
and 3, preparing the composite material, namely putting the non-hydrolytic water-soluble zinc salt, weak base and water into a beaker, uniformly stirring, putting the porous silicon treated in the step 2 into the beaker, transferring the porous silicon into a reaction kettle, putting the reaction kettle into an incubator, and carrying out heat preservation for 5-10h at 90 ℃.
2. The method for preparing the self-supporting porous silicon/ZnO composite material according to claim 1, wherein the etching solution in the step 1 is a hydrofluoric acid ethanol solution, and the volume ratio of hydrofluoric acid to absolute ethanol is 1: 1.
3. the method for preparing the self-supporting porous silicon/ZnO composite material according to claim 1, wherein the current density of the step-by-step alternating in the step 1 is 30mA/cm2、80mA/cm2And the etching time is 30min and 1 min.
4. The method for preparing a self-supporting porous silicon/ZnO composite material according to claim 1, wherein in the step 2, the zinc acetate solution is prepared from a zinc acetate dihydrate and absolute ethyl alcohol, and the concentration is 0.08-0.16 mol/L.
5. The method as claimed in claim 1, wherein the temperature of the high temperature heat preservation in step 2 is controlled to be at 340-380 ℃.
6. The method for preparing the self-supporting porous silicon/ZnO composite material according to claim 1, wherein in the step 2, the high-temperature heat preservation time is controlled to be 20-40 min.
7. The method for preparing a self-supporting porous silicon/ZnO composite material as claimed in claim 1, wherein in the step 3, the non-hydrolyzable water-soluble zinc salt is nitrate or sulfate.
8. The method for preparing a self-supporting porous silicon/ZnO composite material as claimed in claim 1, wherein in the step 3, the weak base is ammonia or urea.
9. The method for preparing self-supporting porous silicon/ZnO composite material according to claim 1, wherein in step 3, after the non-hydrolyzable water soluble zinc salt, the weak base and the water are stirred and mixed uniformly, the pH of the solution is controlled to be between 10 and 11.
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