CN114551120A - Preparation method of metal oxide nanosheet - Google Patents
Preparation method of metal oxide nanosheet Download PDFInfo
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- CN114551120A CN114551120A CN202210038912.2A CN202210038912A CN114551120A CN 114551120 A CN114551120 A CN 114551120A CN 202210038912 A CN202210038912 A CN 202210038912A CN 114551120 A CN114551120 A CN 114551120A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 67
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 54
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 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 32
- 239000002243 precursor Substances 0.000 claims description 29
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 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 6
- 239000002055 nanoplate Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 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
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 8
- 238000013508 migration Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 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
- 238000010438 heat treatment Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 12
- 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
- 239000010949 copper Substances 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
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910003266 NiCo Inorganic materials 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000006260 foam Substances 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 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
- 239000011261 inert gas Substances 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 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
- 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
- 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
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
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 electrode materials of super capacitors, in particular to a preparation method of a metal oxide nanosheet. According to the invention, the metal oxide nanosheets are prepared by adopting the electrolyte at a specific temperature, 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 nanosheets prepared by the preparation method provided by the invention are uniform in 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 1A/g charge-discharge cycle for 2000 times, and the metal oxide nanosheets have obvious redox peaks and charge-discharge platforms and have excellent pseudocapacitance characteristics.
Description
Technical Field
The invention relates to the field of electrode materials of super capacitors, 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 characteristics of quick charge and discharge of the capacitor and the energy storage characteristic of the battery. In the charging/discharging process of the super capacitor, two reactions mainly occur, one is a physical reaction process of double electric layer charging and discharging, and the other is a rapid and reversible electrochemical reaction process occurring on the surface of an electrode. The super capacitor has a high power density (10) compared to conventional capacitors and rechargeable batteries2～104kW/kg), long cycle life, wide working temperature range (-40-65 ℃), green environmental protection and the like.
Supercapacitors can be classified by mechanism into double layer supercapacitors and pseudocapacitance supercapacitors. The electrode material of the double electric layer super capacitor mainly comprises carbon material electrode materials such as carbon nanofiber, carbon aerogel, carbon nanotube and the like; the electrode material of the pseudocapacitance 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 is2O4The cobalt and nickel-containing metal oxide electrode materials can rapidly generate reversible redox reaction, the electrode reaction can go deep into the electrode, and energy can be stored in a two-dimensional space, so that the electrode material has high faradaic capacitance and energy density. However, the existing metal oxide electrode material containing cobalt and nickel has the phenomenon of uneven deposition on the working electrode during electrodeposition.
Disclosure of Invention
The application aims to overcome the defects in the prior art, and provides a preparation method of a metal oxide nanosheet.
A preparation method of metal oxide nanosheets comprises the following steps: electrodepositing a nitrate electrolyte at 0-15 ℃ to obtain a metal hydroxide precursor, washing, drying, and then sintering in a tube-type manner to obtain a metal oxide nanosheet, wherein cations in the nitrate electrolyte comprise cobalt, nickel and M, wherein M is one of Fe, Mn, Cu or Zn, and the molar ratio of cobalt to nickel to M is 2-x: 1+ y: x-y, -0.3< x <0.3, -0.3< y <0.3, x ≧ y.
Compared with the existing method, the preparation method of the metal oxide nanosheet provided by the invention has the following advantages:
the inventor finds that when electrodeposition is carried out at normal temperature, the ion migration rates of cobalt and nickel are different, and the deposition uniformity performance on the working electrode is further influenced. The fundamental reason is assumed that cobalt and nickel are both hexacoordinate ions in an aqueous solution, and when an electrodeposition reaction is performed, the distance between the coordinated ions and a central atom is different, so that the radius of the ions is different, and the migration rate of the ions is further influenced.
The inventor carries out intensive research on the change trends of the migration rates of cobalt and nickel ions at different temperatures, finds that the deposition amounts of the cobalt and nickel ions on a working electrode are small when the temperatures are higher than 0-15 ℃ and higher than 35 ℃ by measuring the deposition quality of the cobalt and nickel ions at different temperatures, further speculates that the coordination form of the cobalt and nickel complex ions is gradually transferred from an inner rail type to an outer rail type along with the increase of the temperature within the range of 15-35 ℃, and has different deposition rates of the cobalt and nickel ions within the temperature range due to different numbers of electrons of 3d rails of the cobalt and nickel ions and different temperature trends of the hybrid rails transferred from the inner rail type to the outer rail type, thereby influencing the uniform deposition performance of the cobalt and nickel ions on the working electrode. In addition, the inventor researches and discovers that when the temperature is higher than 35 ℃, the migration rate of cobalt and nickel ions is too high, so that the grown nano structure is coarse, and the performance of the prepared nano sheet is poor, therefore, the invention selects the electrolyte with the temperature of 0-15 ℃ for electrodeposition. Meanwhile, the electrolyte at the specific temperature is matched with tubular sintering, so that the specific capacitance, the electrochemical energy storage performance and other performances of the nanosheets 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 0-10 ℃.
The difference of the ion migration rates of cobalt and nickel at the preferable temperature is smaller, the deposition is more uniform, and the performance of the metal oxide nanosheet can be further improved.
Preferably, the concentration of cobalt ions in the nitrate electrolyte is 0.1-50 mmol/L.
Preferably, the electrodeposition is constant potential electrodeposition, wherein the deposition potential is-0.5V to-1.2V, and the deposition time is 1-30 min.
Preferably, the tubular sintering comprises 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 tubular sintering further comprises sintering under the protection of inert gas.
By controlling the tube sintering conditions as described above, the specific capacity of the metal oxide nanosheets and the capacity retention rate after charge and discharge cycles can be further improved.
The invention also provides a metal oxide nanosheet prepared by the preparation method of the metal oxide nanosheet.
The metal oxide nanosheets prepared by the preparation method have uniform particle size distribution, the specific capacitance under the current density of 0.5A/g reaches more than 1100F/g, the specific capacitance under the current density of 5A/g reaches more than 600F/g, the capacity is kept at more than 85% after 1A/g charge-discharge cycle for 2000 times, and the metal oxide nanosheets have obvious redox peaks and charge-discharge platforms and have excellent pseudocapacitance characteristics.
Drawings
FIG. 1 is a temperature variation curve of the migration rate of nickel and cobalt ions;
FIG. 2 is a scanning electron micrograph of metal oxide nanoplates prepared in example 1 and comparative example 1;
FIG. 3 is a cyclic voltammetry test chart of metal oxide nanosheets prepared in example 1 and comparative example 1 at different scanning speeds;
fig. 4 is a constant current charge and discharge test chart of the metal oxide nanosheets prepared in example 1 and comparative example 1 under different current densities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 by using a three-electrode system consisting of a 2cm x 2cm foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode at 10 ℃ to obtain a nickel-cobalt double metal hydroxide precursor on foamed nickel, wherein the potential of electrodeposition is-1.0V, and the time is 10 min;
step two, washing a nickel-cobalt double-metal hydroxide precursor on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the dried nickel-cobalt double-metal hydroxide precursor into a quartz tube, heating to 300 ℃ at the heating rate of 1 ℃/min in the atmosphere of argon, and preserving heat for 2 hours to obtain an ultrathin mesoporous nanosheet, wherein the component of the nanosheet is NiCo through detection2O4。
Example 2:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 by using a three-electrode system consisting of a 2cm x 2cm foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode at 0 ℃ to obtain a nickel-cobalt double metal hydroxide precursor on foamed nickel, wherein the potential of electrodeposition is-1.0V, and the time is 10 min;
step two, washing a nickel-cobalt double-metal hydroxide precursor on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the dried nickel-cobalt double-metal hydroxide precursor into a quartz tube, heating to 300 ℃ at the heating rate of 1 ℃/min in the atmosphere of argon, and preserving heat for 2 hours to obtain an ultrathin mesoporous nanosheet, wherein the component of the nanosheet is NiCo through detection2O4。
Example 3:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 by using a three-electrode system consisting of a 2cm x 2cm copper foam working electrode, a platinum sheet counter electrode and a silver-silver chloride reference electrode at 10 ℃ to obtain a nickel-cobalt double metal hydroxide precursor on the foam copper, wherein the potential of the electrodeposition is-0.5V, and the time is 20 min;
step two, washing a nickel-cobalt double-metal hydroxide precursor on the foamy copper by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the precursor into a quartz tube, heating to 400 ℃ at the heating rate of 8 ℃/min in the atmosphere of argon, preserving the temperature for 1h to obtain an ultrathin mesoporous nanosheet, and detecting that the component of the nanosheet is NiCo2O4。
Example 4:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 electrolyte, and performing electrodeposition by using a three-electrode system consisting of a 2cm x 2cm foamy copper working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode at 0 ℃ to obtain a nickel-cobalt double metal hydroxide precursor on foamy copper, wherein the potential of electrodeposition is-1.2V, and the time is 8 min;
step two, washing a nickel-cobalt double-metal hydroxide precursor on the foamy copper by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the precursor into a quartz tube, heating to 350 ℃ at the heating rate of 5 ℃/min in the atmosphere of argon, preserving the temperature for 1.5h to obtain an ultrathin mesoporous nanosheet, and detecting that the component of the nanosheet is NiCo2O4。
Example 5:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 on foamed nickel by using a three-electrode system consisting of a 2cm multiplied by 2cm foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode at 10 ℃ to obtain a precursor of the multi-metal hydroxide of nickel, cobalt and manganese, wherein the potential of the electrodeposition is-1.0V, and the time is 10 min;
step two, washing the multi-metal hydroxide precursor of nickel, cobalt and manganese on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the washed precursor into a quartz tube, heating to 300 ℃ at the heating rate of 1 ℃/min in the atmosphere of argon, and preserving the temperature for 2 hours to obtain the ultrathin mesoporous nanosheet, wherein the component of the nanosheet is Ni through detection0.9Co2Mn0.1O4。
Example 6:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel, cobalt and copper multi-metal hydroxide precursor on the foamed nickel, wherein the potential of the electrodeposition is-1.0V, and the time is 10 min;
step two, washing nickel, cobalt and copper multi-metal hydroxide precursors on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the precursors into a quartz tube, heating to 300 ℃ at the heating rate of 1 ℃/min in the atmosphere of argon, preserving the temperature for 2 hours to obtain ultrathin mesoporous nanosheets, and detecting that the components of the nanosheets are Ni0.9Co2Cu0.1O4。
Example 7:
the embodiment provides a preparation method of a metal oxide nanosheet, which comprises the following steps:
firstly, 0.5239g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate, 0.0808g of iron nitrate nonahydrate and 500mL of deionized water are mixed to prepare electrolyte, and a three-electrode system consisting of a 2cm multiplied by 2cm foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode is used for electrodeposition at 10 ℃ to obtain a nickel, cobalt and iron multi-metal hydroxide precursor on foamed nickel, wherein the potential of electrodeposition is-1.0V, and the time is 10 min;
step two, washing the nickel, cobalt and iron multi-metal hydroxide precursor on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, then putting into a quartz tube, heating to 300 ℃ at the heating rate of 1 ℃/min in the atmosphere of argon, and preserving heat for 2 hours to obtain the ultrathin mesoporous nanosheet, wherein the component of the nanosheet is NiCo through detection1.8Fe0.2O4。
Example 8:
the embodiment provides a preparation method of a metal oxide nanosheet, 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 foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode to obtain a nickel, cobalt and zinc multi-metal hydroxide precursor on the foamed nickel, wherein the potential of the electrodeposition is-1.0V, and the time is 10 min;
step two, washing the nickel, cobalt and zinc multi-metal hydroxide precursor on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying, putting the precursor into a quartz tube, heating to 300 ℃ at the heating rate of 1 ℃/min in the atmosphere of argon, and preserving the temperature for 2 hours to obtain the ultrathin mesoporous nanosheet, wherein the component of the nanosheet is Ni through detection0.9Co2Zn0.1O4。
Comparative example 1:
the electrodeposition temperature in example 1 was adjusted to 20 ℃ without changing the other preparation methods.
Comparative example 2:
the electrodeposition temperature in example 1 was adjusted to 10 ℃ to 30 ℃ and the other preparation methods were not changed.
Comparative example 3:
the electrodeposition temperature in example 1 was adjusted to 35 ℃ at 10 ℃ and the other preparation methods were not changed.
Comparative example 4:
the preparation method of the metal oxide nanosheet provided in embodiment 1 omits a tubular sintering step, and the others are unchanged, specifically:
mixing 0.5821g of cobalt nitrate hexahydrate, 0.2908g of nickel nitrate hexahydrate and 500mL of deionized water to prepare electrolyte, and performing electrodeposition by using a three-electrode system consisting of a 2cm x 2cm foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode at 10 ℃ to obtain a nickel-cobalt double metal hydroxide precursor on foamed nickel, wherein the potential of electrodeposition is-1.0V, and the time is 10 min;
step two, washing a nickel-cobalt double-metal hydroxide precursor on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying to obtain an ultrathin mesoporous nanosheet, and detecting that the component of the nanosheet is NiCo2O4。
Comparative example 5:
the preparation method of the metal oxide nanosheet provided in embodiment 5 omits a tubular sintering step, and the others are unchanged, specifically:
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 on foamed nickel by using a three-electrode system consisting of a 2cm multiplied by 2cm foamed nickel working electrode, a platinum sheet counter electrode and a saturated calomel reference electrode at 10 ℃ to obtain a precursor of the multi-metal hydroxide of nickel, cobalt and manganese, wherein the potential of the electrodeposition is-1.0V, and the time is 10 min;
step two, washing the multi-metal hydroxide precursor of nickel, cobalt and manganese on the foamed nickel by using deionized water and absolute ethyl alcohol under the assistance of ultrasonic waves, drying to obtain the ultrathin mesoporous nanosheet, and detecting that the component of the nanosheet is Ni0.9Co2Mn0.1O4。
In order to better illustrate that the metal oxide nanosheets provided by the embodiments of the present invention have excellent performance, the performance tests of the metal oxide nanosheets prepared in the embodiments 1 to 8 and the comparative examples 1 to 5 are respectively performed, and the test results are shown in table 1.
TABLE 1
As is apparent from Table 1, the specific capacitance of the metal oxide nanosheet prepared in the example of the present invention at a current density of 0.5A/g is more than 1100F/g, the specific capacitance at a current density of 5A/g is more than 600F/g, and the capacity is maintained at more than 85% after 2000 times of charge-discharge cycles of 1A/g. As can be seen from comparative examples 1 to 5, the above-mentioned performance indexes are remarkably deteriorated by increasing the electrodeposition temperature or omitting the tubular sintering step. Therefore, the preparation method of the metal oxide nanosheet 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 nanosheets prepared in example 1 and comparative example 1 are subjected to electron microscope scanning, cyclic voltammetry and charging and discharging tests respectively, Scanning Electron Microscope (SEM) photographs are shown in fig. 2, wherein the top left and bottom left are electron microscope photographs of the metal oxide nanosheets magnified ten thousand times, and the top right and bottom right are electron microscope photographs of the metal oxide nanosheets magnified fifty thousand times, so that the metal oxide nanosheets prepared in the embodiment of the present invention have uniform particle size distribution; as shown in fig. 3, 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 integrated area of the CV curve of example 1 is larger than that of comparative example 1, which indicates that the metal oxide nanosheet prepared in example 1 has better specific capacitance; as shown in fig. 4, it can be seen that the metal oxide nanosheet prepared in example 1 has a longer discharge time, indicating that example 1 has excellent electrochemical energy storage performance; therefore, the metal oxide nanosheet prepared by the method disclosed by the invention is uniform in particle size distribution, has an obvious redox peak and a charging and discharging platform, and shows that the metal oxide nanosheet has excellent pseudocapacitance characteristics.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of a metal oxide nanosheet is characterized by comprising the following steps: electrodepositing a nitrate electrolyte at 0-15 ℃ to obtain a metal hydroxide precursor, washing, drying, and then sintering in a tube-type manner to obtain a metal oxide nanosheet, wherein 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 cobalt to nickel to M is 2-x: 1+ y: x-y, -0.3< x <0.3, -0.3< y <0.3, x ≧ y.
2. A method for producing metal oxide nanoplates as in claim 1, wherein the temperature of the electrolyte is 0-10 ℃.
3. A method for producing metal oxide nanoplates as in claim 1, wherein the concentration of cobalt ions in the nitrate electrolyte is 0.1-50 mmol/L.
4. A process for the preparation of metal oxide nanoplates as in claim 1, wherein the electrodeposition is potentiostatic electrodeposition, wherein the deposition potential is from-0.5V to-1.2V and the deposition time is from 1 to 30 min.
5. A method of making metal oxide nanoplates as in claim 1, wherein the tubular sintering comprises ramping up to 250-450 ℃ at a ramp rate of 1-10 ℃/min.
6. A process for the preparation of metal oxide nanoplates as in claim 5, wherein the tubular sintering is carried out for a sintering time of 1 to 3 hours.
7. A metal oxide nanosheet produced by the method for producing a metal oxide nanosheet according to any one of claims 1 to 6.
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