CN114551120B - Preparation method of metal oxide nanosheets - Google Patents
Preparation method of metal oxide nanosheets Download PDFInfo
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- CN114551120B CN114551120B CN202210038912.2A CN202210038912A CN114551120B CN 114551120 B CN114551120 B CN 114551120B CN 202210038912 A CN202210038912 A CN 202210038912A CN 114551120 B CN114551120 B CN 114551120B
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 61
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 51
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 55
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 238000004070 electrodeposition Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- 239000002064 nanoplatelet Substances 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 239000006260 foam Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229910001453 nickel ion Inorganic materials 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910003266 NiCo Inorganic materials 0.000 description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage 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
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- 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
Abstract
The invention relates to the field of supercapacitor electrode materials, in particular to a preparation method of a metal oxide nanosheet. According to the invention, the electrolyte with a specific temperature is adopted to prepare the metal oxide nano-sheet, so that the technical problem of uneven deposition caused by different ion migration rates of nickel and cobalt can be effectively solved. The metal oxide nano-sheet prepared by the preparation method provided by the invention has uniform particle size distribution, the specific capacitance at the current density of 0.5A/g reaches more than 1100F/g, the specific capacitance at the current density of 5A/g reaches more than 600F/g, the capacity is kept at more than 85% after 2000 charge and discharge cycles of 1A/g, and the metal oxide nano-sheet has obvious oxidation-reduction peaks and charge and discharge platforms and excellent pseudo-capacitance characteristics.
Description
Technical Field
The invention relates to the field of supercapacitor electrode materials, in particular to a preparation method of a metal oxide nanosheet.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristic of rapid charge and discharge of the capacitor and the energy storage characteristic of the battery. In the process of charging/discharging, two reactions mainly occur in the supercapacitor, one is a physical reaction process of electric double layer charging/discharging, and the other is a rapid and reversible electrochemical reaction process occurring on the surface of an electrode. Compared with conventional capacitors and rechargeable batteries, supercapacitors have a high power density (10 2 ～10 4 kW/kg), long cycle life, wide working temperature range (-40-65 ℃), environmental protection and the like.
Supercapacitors can be classified into electric double layer supercapacitors and pseudocapacitance supercapacitors by mechanism. The electrode material of the double-layer supercapacitor mainly comprises carbon material electrode materials such as carbon nanofiber, carbon aerogel, carbon nanotube and the like; the electrode material of the pseudo-capacitor super capacitor mainly comprises metal oxide electrode materials such as nickel oxide, manganese oxide, cobalt oxide and the like, and conductive polymer electrode materials such as polyaniline, polythiophene, polypyrrole and the like. Wherein NiCo 2 O 4 The metal oxide electrode material containing cobalt and nickel can quickly generate reversible oxidation-reduction reaction, the electrode reaction can go deep into the electrode, and energy can be stored in two-dimensional space, so that the electrode material has high Faraday quasi-capacitance and energy density. However, in the conventional metal oxide electrode material containing cobalt and nickel, there is a phenomenon that deposition is not uniform on the working electrode when electrodeposition is performed.
Disclosure of Invention
The purpose of the application is to overcome the defects existing in the prior art, and provide a preparation method of the metal oxide nano-sheet, wherein the migration rate trend of cobalt and nickel ions is the same by adopting the preparation method, the metal oxide nano-sheet is uniformly deposited on a working electrode, and the specific capacitance and the electrochemical energy storage performance of the metal oxide nano-sheet are obviously improved.
A method for preparing a metal oxide nanosheet, comprising the steps of: electrodepositing nitrate electrolyte at 0-15 ℃ to obtain a metal hydroxide precursor, washing, drying and then performing tube-through sintering to obtain a metal oxide nano-sheet, wherein cations in the nitrate electrolyte comprise cobalt, nickel and M, M is one of Fe, mn, cu or Zn, and the molar ratio of the cobalt to the nickel to the M is 2-x:1+y: x-y, -0.3< x <0.3, -0.3< y <0.3, x is not less than y.
Compared with the existing method, the preparation method of the metal oxide nano-sheet provided by the invention has the following advantages:
the inventors found through researches that when electrodeposition is performed at normal temperature, ion migration rates of cobalt and nickel are different, and thus deposition uniformity performance on a working electrode is affected. The root cause is presumed that cobalt and nickel are hexacoordinated ions in an aqueous solution, and when the electrodeposition reaction is performed, the distances between the coordinated ions and the central atoms are different, so that the radius of the ions is different, and the migration rate of the ions is affected.
The inventors conducted intensive studies on the variation trend of the migration rate of cobalt and nickel ions at different temperatures, found that the difference of the deposition rates of cobalt and nickel ions on the working electrode is small at 0-15 ℃ and above 35 ℃ by measuring the deposition quality of cobalt and nickel at different temperatures, further speculated that the coordination form of cobalt and nickel complex ions is gradually transferred from an inner rail type to an outer rail type along with the rising of the temperature within the range of 15-35 ℃, and the temperature trend of the transfer of the hybridization rail from the inner rail type to the outer rail type is also different due to the different 3d electron numbers of the cobalt and nickel ions, so that the deposition rates of cobalt and nickel ions are different within the temperature range, and further the deposition uniformity performance of cobalt and nickel ions on the working electrode is affected. Moreover, the inventor researches and discovers that when the temperature is higher than 35 ℃, cobalt and nickel ions have too high migration rate, which can cause coarse grown nano-structures, and the prepared nano-sheet has poor performance, so that the invention selects electrolyte with the temperature of 0-15 ℃ for electrodeposition. Meanwhile, the electrolyte with the specific temperature is matched with tubular sintering, so that the specific capacitance, electrochemical energy storage and other performances of the nano-sheet are synergistically improved.
The nitrate electrolyte may be prepared by dissolving a nitrate corresponding to a cation or a hydrate thereof in water, such as cobalt nitrate, nickel nitrate, iron nitrate, manganese nitrate, copper nitrate, zinc nitrate, or a hydrate thereof.
Preferably, the temperature of the electrolyte is 0 to 10 ℃.
The ion migration rates of cobalt and nickel at the preferable temperature are smaller in difference, the deposition is more uniform, and the performance of the metal oxide nano-sheet can be further improved.
Preferably, the concentration of cobalt ions in the nitrate electrolyte is 0.1-50 mmol/L.
Preferably, the electrodeposition is potentiostatic electrodeposition, wherein the deposition potential is-0.5V to-1.2V, and the deposition time is 1-30 min.
Preferably, the tube sintering includes heating to 250-450 ℃ at a heating rate of 1-10 ℃/min.
Preferably, the sintering time of the tubular sintering is 1-3 h.
Preferably, the tube sintering further comprises sintering under inert gas protection.
By the above-described preferable tubular sintering condition, the specific capacity of the metal oxide nanoplatelets and the capacity retention after charge-discharge cycles can be further improved.
The invention also provides a metal oxide nano-sheet, which is prepared by the preparation method of the metal oxide nano-sheet.
The metal oxide nano-sheet prepared by the preparation method has uniform particle size distribution, the specific capacitance at the current density of 0.5A/g reaches more than 1100F/g, the specific capacitance at the current density of 5A/g reaches more than 600F/g, the capacity is kept at more than 85% after 2000 times of charge-discharge cycles of 1A/g, and the metal oxide nano-sheet has obvious oxidation-reduction peaks and charge-discharge platforms and excellent pseudo-capacitance characteristics.
Drawings
FIG. 1 is a graph showing the temperature change of migration rates of nickel and cobalt ions;
FIG. 2 is a scanning electron microscope image of the metal oxide nanoplatelets prepared in example 1 and comparative example 1;
FIG. 3 is a cyclic voltammetry graph of the metal oxide nanoplatelets prepared in example 1 and comparative example 1 at different scan rates;
fig. 4 is a constant current charge-discharge test chart of the metal oxide nanoplatelets prepared in example 1 and comparative example 1 at different current densities.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel and cobalt bimetallic hydroxide precursor on the foam nickel, wherein the electrodepositing potential is-1.0V, and the time is 10min;
washing nickel and cobalt double metal hydroxide precursors on foam nickel with the aid of deionized water and absolute ethyl alcohol under ultrasonic waves, drying, putting into a quartz tube, heating to 300 ℃ at a heating rate of 1 ℃/min under argon atmosphere, and preserving heat for 2 hours to obtain ultrathin mesoporous nano sheets, wherein the components of the nano sheets are NiCo after detection 2 O 4 。
Example 2:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 0 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel and cobalt bimetallic hydroxide precursor on the foam nickel, wherein the electrodepositing potential is-1.0V, and the time is 10min;
washing nickel and cobalt double metal hydroxide precursors on foam nickel with the aid of deionized water and absolute ethyl alcohol under ultrasonic waves, drying, putting into a quartz tube, heating to 300 ℃ at a heating rate of 1 ℃/min under argon atmosphere, and preserving heat for 2 hours to obtain ultrathin mesoporous nano sheets, wherein the components of the nano sheets are NiCo after detection 2 O 4 。
Example 3:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm copper foam working electrode, a platinum sheet counter electrode and a silver-silver chloride reference electrode to obtain a nickel-cobalt bimetallic hydroxide precursor on foam copper, wherein the electrodepositing potential is-0.5V and the time is 20min;
step two, washing nickel and cobalt double metal hydroxide precursors on foam copper with the aid of deionized water and absolute ethyl alcohol under ultrasonic waves, drying, putting into a quartz tube, heating to 400 ℃ at a heating rate of 8 ℃/min under argon atmosphere, and preserving heat for 1h to obtain ultrathin mesoporous nano sheets, wherein the components of the nano sheets are NiCo after detection 2 O 4 。
Example 4:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 5.821g of cobalt nitrate hexahydrate, 2.908g of nickel nitrate hexahydrate and 500mL of deionized water to prepare an electrolyte, and performing electrodeposition at 0 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam copper working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel-cobalt bimetallic hydroxide precursor on the foam copper, wherein the electrodeposited potential is-1.2V, and the time is 8min;
step two, washing nickel and cobalt double metal hydroxide precursors on the foam copper with the aid of ultrasonic waves by using deionized water and absolute ethyl alcohol, drying and then putting intoIn a quartz tube, under the atmosphere of argon, heating to 350 ℃ at a heating rate of 5 ℃/min, and preserving heat for 1.5 hours to obtain an ultrathin mesoporous nano sheet, wherein the nano sheet is detected to be NiCo in the components 2 O 4 。
Example 5:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2617g of nickel nitrate hexahydrate, 0.0287g of manganese nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a multi-metal hydroxide precursor of nickel, cobalt and manganese on the foam nickel, wherein the electrodeposited potential is-1.0V, and the time is 10min;
washing nickel, cobalt and manganese polymetallic hydroxide precursors on foam nickel with the aid of deionized water and absolute ethyl alcohol under ultrasonic waves, drying, putting into a quartz tube, heating to 300 ℃ at a heating rate of 1 ℃/min under an argon atmosphere, and preserving heat for 2 hours to obtain ultrathin mesoporous nano sheets, wherein the components of the nano sheets are Ni after detection 0.9 Co 2 Mn 0.1 O 4 。
Example 6:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2617g of nickel nitrate hexahydrate, 0.0295g of copper nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel, cobalt and copper polymetallic hydroxide precursor on the foam nickel, wherein the electrodeposited potential is-1.0V, and the time is 10min;
step two, washing nickel, cobalt and copper multi-metal hydroxide precursors on foam nickel with the aid of ultrasonic waves by using deionized water and absolute ethyl alcohol, drying, putting into a quartz tube, and placing at 1 ℃ in an argon atmosphereHeating to 300 ℃ at a heating rate of/min, and preserving heat for 2 hours to obtain ultrathin mesoporous nanosheets, wherein the nanosheets are detected to contain Ni as components 0.9 Co 2 Cu 0.1 O 4 。
Example 7:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5239g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate, 0.0808g of ferric nitrate nonahydrate and 500mL of deionized water to prepare an electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel, cobalt and iron polymetallic hydroxide precursor on the foam nickel, wherein the electrodeposited potential is-1.0V for 10min;
washing nickel, cobalt and iron multi-metal hydroxide precursors on foam nickel with the aid of deionized water and absolute ethyl alcohol under ultrasonic waves, drying, putting into a quartz tube, heating to 300 ℃ at a heating rate of 1 ℃/min under an argon atmosphere, and preserving heat for 2 hours to obtain ultrathin mesoporous nano sheets, wherein the components of the nano sheets are NiCo after detection 1.8 Fe 0.2 O 4 。
Example 8:
the embodiment provides a preparation method of a metal oxide nano sheet, which comprises the following steps:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2617g of nickel nitrate hexahydrate, 0.0297g of zinc nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel, cobalt and zinc polymetallic hydroxide precursor on the foam nickel, wherein the electrodeposited potential is-1.0V, and the time is 10min;
step two, washing nickel, cobalt and zinc multi-metal hydroxide precursors on foam nickel with the aid of ultrasonic waves by using deionized water and absolute ethyl alcohol, drying, putting into a quartz tube, and heating to 300 ℃ at a heating rate of 1 ℃/min under the atmosphere of argonAfter heat preservation for 2 hours, an ultrathin mesoporous nano sheet is obtained, and the nano sheet is detected to contain Ni as the component 0.9 Co 2 Zn 0.1 O 4 。
Comparative example 1:
the electrodeposition temperature of example 1 was adjusted to 20℃at 10℃with other preparation methods unchanged.
Comparative example 2:
the electrodeposition temperature of example 1 was adjusted to 30℃at 10℃with other preparation methods unchanged.
Comparative example 3:
the electrodeposition temperature of example 1 was adjusted to 35℃at 10℃with the other preparation methods unchanged.
Comparative example 4:
the tubular sintering step is omitted in the preparation method of the metal oxide nanosheets provided in example 1, and the other steps are as follows:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel and cobalt bimetallic hydroxide precursor on the foam nickel, wherein the electrodepositing potential is-1.0V, and the time is 10min;
step two, washing nickel and cobalt double metal hydroxide precursors on foam nickel with the aid of deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying to obtain ultrathin mesoporous nano sheets, and detecting that the components of the nano sheets are NiCo 2 O 4 。
Comparative example 5:
the tubular sintering step is omitted in the preparation method of the metal oxide nanosheets provided in example 5, and the other steps are as follows:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2617g of nickel nitrate hexahydrate, 0.0287g of manganese nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition at 10 ℃ by using a three-electrode system consisting of a 2cm multiplied by 2cm foam nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a multi-metal hydroxide precursor of nickel, cobalt and manganese on the foam nickel, wherein the electrodeposited potential is-1.0V, and the time is 10min;
step two, washing nickel, cobalt and manganese polymetallic hydroxide precursors on foam nickel with the aid of deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying to obtain ultrathin mesoporous nano sheets, and detecting that the components of the nano sheets are Ni 0.9 Co 2 Mn 0.1 O 4 。
In order to better illustrate the excellent performance of the metal oxide nanoplatelets provided in the examples of the present invention, the following performance tests were performed on the metal oxide nanoplatelets prepared in examples 1 to 8 and comparative examples 1 to 5, respectively, and the test results are shown in table 1.
TABLE 1
As apparent from Table 1, the specific capacitance of the metal oxide nanoplatelets prepared in the examples of the present invention reaches over 1100F/g at a current density of 0.5A/g, and at a current density of 5A/g, reaches over 600F/g, and the capacity remains over 85% after 2000 charge and discharge cycles of 1A/g. As can be seen from comparative examples 1 to 5, the above performance indexes are significantly deteriorated by increasing the electrodeposition temperature or omitting the tube sintering step. Therefore, the preparation method of the metal oxide nano-sheet provided by the invention can effectively solve the technical problem of uneven deposition caused by different ion migration rates of nickel and cobalt.
Meanwhile, the metal oxide nano-sheets prepared in the embodiment 1 and the comparative embodiment 1 are respectively subjected to electron microscope scanning, cyclic voltammetry and charge-discharge testing, scanning Electron Microscope (SEM) pictures are shown in figure 2, the upper left and lower left are electron microscope pictures of the metal oxide nano-sheets amplified by ten thousand times, and the upper right and lower right are electron microscope pictures of the metal oxide nano-sheets amplified by fifty thousand times, so that the metal oxide nano-sheets prepared in the embodiment of the invention are uniform in particle size distribution; the cyclic voltammetry test is shown in fig. 3, and it can be seen that when the scanning rate is increased, the peak current density is also increased, and under the same scanning rate, the integral area of the CV curve of example 1 is larger than that of comparative example 1, which indicates that the metal oxide nano-sheet prepared in example 1 has better specific capacitance; constant voltage charge and discharge test as shown in fig. 4, it can be seen that the metal oxide nanoplatelets prepared in example 1 have longer discharge time, indicating that example 1 has excellent electrochemical energy storage performance; therefore, the metal oxide nano-sheet prepared by the method has uniform particle size distribution, obvious oxidation-reduction peaks and charge-discharge platforms, and shows that the metal oxide nano-sheet has excellent pseudo-capacitance characteristics.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (3)
1. The preparation method of the metal oxide nanosheets is characterized by comprising the following steps: electrodepositing the nitrate electrolyte at 0-15 ℃ to obtain a metal hydroxide precursor, washing, drying, and performing tube-type sintering to obtain a metal oxide nano-sheet;
the cations in the nitrate electrolyte are cobalt, nickel and M, wherein M is one of Fe, mn, cu or Zn, and the molar ratio of the cobalt to the nickel to the M is 2-x:1+y: x-y, -0.3< x <0.3, -0.3< y <0.3, x is greater than or equal to y; the concentration of cobalt ions in the nitrate electrolyte is 0.1-50 mmol/L;
the electrodeposition is constant potential electrodeposition, wherein the deposition potential is-0.5V to-1.2V, and the deposition time is 1-30 min;
the tube sintering comprises the step of heating to 250-450 ℃ at a heating rate of 1-10 ℃/min.
2. The method for preparing metal oxide nanoplatelets according to claim 1, wherein the temperature of the electrolyte is 0-10 ℃.
3. The method for preparing a metal oxide nanosheet according to claim 1, wherein the sintering time of the tubular sintering is 1-3 hours.
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