CN108987120B - Method for preparing ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide - Google Patents
Method for preparing ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 109
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 238000005530 etching Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- -1 transition metal selenide Chemical class 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 16
- 239000011565 manganese chloride Substances 0.000 claims description 16
- 229940099607 manganese chloride Drugs 0.000 claims description 16
- 235000002867 manganese chloride Nutrition 0.000 claims description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 claims description 7
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 5
- CPYJQJCFBJRNQD-UHFFFAOYSA-N [Se].[Mn].[Ni] Chemical compound [Se].[Mn].[Ni] CPYJQJCFBJRNQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 229910052711 selenium Inorganic materials 0.000 description 10
- 239000011669 selenium Substances 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 150000002697 manganese compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XIDSJQZYQXRYHQ-UHFFFAOYSA-N nickel(2+);selenium(2-) Chemical compound [Ni+2].[Se-2] XIDSJQZYQXRYHQ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 101100460704 Aspergillus sp. (strain MF297-2) notI gene Proteins 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 description 1
- IJUKXQRCJABGNO-UHFFFAOYSA-N [Se].[Ni]=[Se] Chemical compound [Se].[Ni]=[Se] IJUKXQRCJABGNO-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
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- 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
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Abstract
The invention discloses a method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide, and relates to the technical field of electrode materials of supercapacitors. The invention aims to solve the problems that the existing transition metal selenide nanosheet electrode material has an unreasonable structure, and cannot have porosity if the material is an ultrathin nanosheet structure, so that the ion mobility is influenced, and the electrode material can contact with an active site; if the nano sheet is a porous nano sheet, the thickness is too thick, the contact active sites are few, the energy storage is low, and the capacitance performance is low. The method comprises the following steps: firstly, preparing a reaction solution; secondly, preparing a manganese-doped nickel hydroxide nanosheet array; thirdly, selenizing; and fourthly, acid etching treatment, namely completing the method for preparing the ultrathin porous nickel selenide nanosheet array by etching the manganese-doped nickel hydroxide. The invention provides a method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide.
Description
Technical Field
The invention belongs to the technical field of electrode materials of super capacitors.
Background
Because the traditional energy is gradually exhausted and the environment is increasingly worsened, the development of novel energy storage devices becomes a key problem to be solved urgently. Among them, owing to the extremely high power density and the extremely long cycle life, a supercapacitor, which is one of the novel energy storage devices, has become a hot point of research. The electrode material is used as a key factor for determining the performance of the super capacitor and becomes a breakthrough for solving the energy and environment problems. The transition metal oxide and the transition metal hydroxide are the most widely researched supercapacitor electrode materials at present due to rich element reserves, low price and outstanding capacitance performance. However, the low conductivity and low accessible active sites of the currently developed transition metal compounds are limited, so that the capacitance and energy density of the current super capacitor are still low, and the commercial application is difficult to meet.
With the progress of research, transition metal sulfide, phosphide and selenide nanostructure are gradually developed to improve the capacitance performance of the super capacitor. Among all transition metal compounds, the transition metal selenide is generally much lower in resistance than its oxide, even sulfide, phosphide, etc., due to the extremely high conductivity of selenium itself, and the electrochemical activity of the transition metal selenide is also stronger than that of other types of compounds due to the less strong oxidizing property of selenium. Therefore, the transition metal selenide is an excellent electrode material of the super capacitor. The other important factor influencing the capacitive performance of the electrode material is the microstructure of the material after the material is removed, and the open porous structure can greatly promote the migration rate of electrolyte ions and improve the capacitive performance. In addition, the porous ultrathin two-dimensional nanosheets can expose out contact active sites far more than those of other structures, and the capacitance performance can be greatly enhanced.
The reported scientific achievements and patents include nickel sulfide nanosheets, honeycomb nickel selenide, nickel diselenide nanosheets with selenium-rich surfaces and the like which are applied to supercapacitors. Although the research utilizes the advantages of transition metal selenide and sulfide, the nano-sheet of the existing transition metal selenide electrode material is notIs a porous structure, the thickness of the nano-sheet is about dozens of nanometers, and the corresponding maximum capacitance value is about 750F/g (cobalt nickel selenide hollow sphere, NiCoSe)2Hollow Sub-Microspheres), 2435F/g (nickel sulfide array, Ni3S23D-Network), 674F/g (cobalt selenide nanowire array, Hollow Co)0.85Senowire Array) cannot be further promoted to meet the commercial application. In conclusion, the development of the porous and ultrathin three-dimensional array structure transition metal selenide electrode material with ultrahigh capacitive performance has great significance for improving the energy environment problem.
Disclosure of Invention
The invention aims to solve the problems that the existing transition metal selenide nanosheet electrode material has an unreasonable structure, and cannot have porosity if the material is an ultrathin nanosheet structure, so that the ion mobility is influenced, and the electrode material can contact with an active site; if the nano sheet is a porous nano sheet, the thickness is too thick, the contact active sites are few, the energy storage is low, and the capacitance performance is low, so that the method for preparing the ultrathin porous nickel selenide nano sheet array by etching the manganese-doped nickel hydroxide is provided.
A method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide is carried out according to the following steps:
firstly, preparing a reaction solution:
adding nickel nitrate, manganese chloride and hexadecyl trimethyl ammonium bromide into the mixed solution, and fully mixing to obtain a reaction solution;
the total concentration of the nickel nitrate and the manganese chloride in the reaction liquid is 0.03 mmol/mL-0.05 mmol/mL; the concentration ratio of the nickel nitrate to the manganese chloride is 1 (1-7); the concentration of hexadecyl trimethyl ammonium bromide in the reaction liquid is 0.05 mmol/mL-1.4 mmol/mL; the mixed solution is a mixed solution of methanol and water, and the volume ratio of the methanol to the water in the mixed solution is 1 (1-6);
secondly, preparing a manganese-doped nickel hydroxide nanosheet array:
soaking foamed nickel in the reaction solution, then reacting for 3-48 h at the temperature of 170-190 ℃, taking out the foamed nickel after the reaction is finished, washing, and drying at the temperature of 40-100 ℃ to obtain a manganese-doped nickel hydroxide nanosheet array;
thirdly, selenizing:
adding selenium powder into a sodium borohydride aqueous solution with the concentration of 0.4 mmol/L-1 mmol/L, fully reacting until the solution is clear to obtain a sodium hydroselenide aqueous solution, adding a manganese-doped nickel hydroxide nanosheet array into a reaction kettle containing absolute ethyl alcohol under the nitrogen atmosphere, soaking the reaction kettle in the absolute ethyl alcohol, adding the sodium hydroselenide aqueous solution into the reaction kettle, sealing the reaction kettle, and reacting for 3-24 hours at the temperature of 140-180 ℃ to obtain a selenium nickel-manganese compound;
the molar ratio of the selenium powder to the sodium borohydride is 1 (2-2.5); the volume ratio of the sodium hydrogen selenide aqueous solution to the absolute ethyl alcohol is 1 (8-20);
fourthly, acid etching treatment:
immersing the selenized nickel-manganese compound into dilute hydrochloric acid with the concentration of 0.2-3 mmol/L, standing for 1-6 h, taking out after etching, washing and drying to obtain the ultrathin porous nickel selenide nanosheet array.
The invention has the beneficial effects that:
1. the method takes a manganese-doped nickel hydroxide array as a precursor, and creatively prepares the ultrathin porous nickel selenide nanosheet array with the thickness of about 5nm through two-step etching. In the prior art, a large amount of selenium is introduced into pure nickel hydroxide array selenization, and the original array structure is damaged to a certain extent and a porous structure cannot be obtained. The manganese-doped nickel hydroxide array is difficult to react with selenium ions under the same conditions to be desorbed as nano particles due to the fact that manganese compounds are difficult to react with the selenium ions, a porous structure is generated and a frame structure of nickel is protected due to the fact that the manganese ions are far higher than the hydrolysis equilibrium constant of the nickel ions, the manganese compounds are completely removed through further acid washing, and further more open holes are generated.
2. The ultrathin (5nm) porous nickel selenide nanosheet array grows on the conductive substrate in situ, so that the conductivity of the electrode is greatly enhanced, the cycling stability is improved, and the capacitance performance is improved. More importantly, the nickel selenide has excellent conductivity, and the rapid ion mobility and abundant electrochemical active sites brought by the porous ultrathin nanosheet structure also greatly enhance the capacitance capability of the material. The capacitance value of the super capacitor assembled by the electrode material reaches 3546F/g (3A/g) under three electrodes, and the capacitance value still keeps close to 95 percent after the super capacitor is cycled for 5000 times in a continuous charge-discharge test at 5A/g current density.
3. The method provided by the invention is used for processing the manganese-containing nickel precursor through two-step reaction of selenization and acid washing to obtain the porous nickel selenide nanosheet, and the method is still suitable for other manganese-containing precursors, so that the method has great reference significance for preparing other similar selenide porous nanomaterials.
4. The method has mild reaction conditions and extremely low requirements on equipment, and the used nickel foam, metal salt, selenium powder and the like are common materials or medicines, so the method has low cost and is suitable for large-scale production. In addition, the electrode material in-situ grown on the foamed nickel substrate can be directly used as an electrode, so that the preparation process of the electrode is greatly simplified, the production cost is saved, and the industrial requirement of environmental protection is met.
The invention provides a method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide.
Drawings
Fig. 1 is an SEM photograph of an ultra-thin porous nickel selenide nanosheet array prepared in example one, magnified 5000 times;
FIG. 2 is an AFM image of an ultrathin porous nickel selenide nanosheet array prepared in example one;
FIG. 3 is a graph of the thickness profile corresponding to FIG. 2;
FIG. 4 is a TEM photograph of the ultrathin porous nickel selenide nanosheet array prepared in example one;
FIG. 5 is a HRTEM photograph of the ultrathin porous nickel selenide nanosheet array prepared in example one;
FIG. 6 is an X-ray diffraction pattern of the ultrathin porous nickel selenide nanosheet array prepared in the first example, wherein 1 is a diffraction peak of NiSe, 2 is a diffraction peak of Makinenite NiSe, and 3 is a diffraction peak of metallic nickel;
FIG. 7 is a cyclic voltammetry graph of the ultrathin porous nickel selenide nanosheet array prepared in the first example at different scan rates, with 1mV/s, 2mV/s, 3 at 5mV/s, 4 at 10mV/s, and 5 at 20 mV/s;
fig. 8 is a constant current charge and discharge curve diagram of the ultrathin porous nickel selenide nanosheet array prepared in the first embodiment at different current densities, where 1 is 3A/g, 2 is 4A/g, 3 is 5A/g, 4 is 6A/g, 5 is 8A/g, and 6 is 10A/g;
fig. 9 is a cycle stability curve obtained by the ultra-thin porous nickel selenide nanosheet array prepared in the first embodiment under a 5A/g current density continuous charge-discharge test;
FIG. 10 is a graph of mass to capacitance as a function of current density; 1 is an ultrathin porous nickel selenide nanosheet array prepared in the first example, 2 is an ultrathin porous nickel selenide nanosheet array prepared in the second example, and 3 is a nickel selenide nanosheet array prepared in the third example;
fig. 11 is an SEM photograph of the ultra-thin porous nickel selenide nanosheet array prepared in example one, magnified 20000 times;
fig. 12 is an SEM photograph of the ultra-thin porous nickel selenide nanosheet array prepared in example two, magnified 20000 times;
fig. 13 is an SEM photograph of the nickel selenide nanosheet array prepared in example three at a magnification of 20000 times.
Detailed Description
The first embodiment is as follows: the method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide in the embodiment is carried out according to the following steps:
firstly, preparing a reaction solution:
adding nickel nitrate, manganese chloride and hexadecyl trimethyl ammonium bromide into the mixed solution, and fully mixing to obtain a reaction solution;
the total concentration of the nickel nitrate and the manganese chloride in the reaction liquid is 0.03 mmol/mL-0.05 mmol/mL; the concentration ratio of the nickel nitrate to the manganese chloride is 1 (1-7); the concentration of hexadecyl trimethyl ammonium bromide in the reaction liquid is 0.05 mmol/mL-1.4 mmol/mL; the mixed solution is a mixed solution of methanol and water, and the volume ratio of the methanol to the water in the mixed solution is 1 (1-6);
secondly, preparing a manganese-doped nickel hydroxide nanosheet array:
soaking foamed nickel in the reaction solution, then reacting for 3-48 h at the temperature of 170-190 ℃, taking out the foamed nickel after the reaction is finished, washing, and drying at the temperature of 40-100 ℃ to obtain a manganese-doped nickel hydroxide nanosheet array;
thirdly, selenizing:
adding selenium powder into a sodium borohydride aqueous solution with the concentration of 0.4 mmol/L-1 mmol/L, fully reacting until the solution is clear to obtain a sodium hydroselenide aqueous solution, adding a manganese-doped nickel hydroxide nanosheet array into a reaction kettle containing absolute ethyl alcohol under the nitrogen atmosphere, soaking the reaction kettle in the absolute ethyl alcohol, adding the sodium hydroselenide aqueous solution into the reaction kettle, sealing the reaction kettle, and reacting for 3-24 hours at the temperature of 140-180 ℃ to obtain a selenium nickel-manganese compound;
the molar ratio of the selenium powder to the sodium borohydride is 1 (2-2.5); the volume ratio of the sodium hydrogen selenide aqueous solution to the absolute ethyl alcohol is 1 (8-20);
fourthly, acid etching treatment:
immersing the selenized nickel-manganese compound into dilute hydrochloric acid with the concentration of 0.2-3 mmol/L, standing for 1-6 h, taking out after etching, washing and drying to obtain the ultrathin porous nickel selenide nanosheet array.
The beneficial effects of the embodiment are as follows: 1. in the specific embodiment, the manganese-doped nickel hydroxide array is used as a precursor, and the ultrathin porous nickel selenide nanosheet array with the thickness of about 5nm is creatively prepared through two-step etching. In the prior art, a large amount of selenium is introduced into pure nickel hydroxide array selenization, and the original array structure is damaged to a certain extent and a porous structure cannot be obtained. The manganese-doped nickel hydroxide array is difficult to react with selenium ions under the same conditions to be desorbed as nano particles due to the fact that manganese compounds are difficult to react with the selenium ions, a porous structure is generated and a frame structure of nickel is protected due to the fact that the manganese ions are far higher than the hydrolysis equilibrium constant of the nickel ions, the manganese compounds are completely removed through further acid washing, and further more open holes are generated.
2. The ultrathin (5nm) porous nickel selenide nanosheet array grows on the conductive substrate in situ, so that the conductivity of the electrode is greatly enhanced, the cycling stability is improved, and the capacitance performance is improved. More importantly, the nickel selenide has excellent conductivity, and the rapid ion mobility and abundant electrochemical active sites brought by the porous ultrathin nanosheet structure also greatly enhance the capacitance capability of the material. The capacitance value of the super capacitor assembled by the electrode material of the embodiment reaches 3546F/g (3A/g) under three electrodes, and the capacitance value still keeps close to 95% after the super capacitor is cycled for 5000 times in a continuous charge-discharge test at 5A/g current density.
3. According to the method, the porous nickel selenide nanosheet is obtained by treating the manganese-containing nickel precursor through two steps of reaction of selenization and acid washing, and the method is still suitable for other manganese-containing precursors, so that the method has great reference significance for preparing other similar selenide porous nanomaterials.
4. The specific implementation method has mild reaction conditions and extremely low requirements on equipment, and the used nickel foam, metal salt, selenium powder and the like are common materials or medicines, so that the method is low in cost and suitable for large-scale production. In addition, the electrode material in-situ grown on the foamed nickel substrate can be directly used as an electrode, so that the preparation process of the electrode is greatly simplified, the production cost is saved, and the industrial requirement of environmental protection is met.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the total concentration of the nickel nitrate and the manganese chloride in the reaction liquid in the step one is 0.04 mmol/mL-0.05 mmol/mL. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the concentration ratio of the nickel nitrate to the manganese chloride in the first step is 1 (1-4). The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the concentration of the hexadecyl trimethyl ammonium bromide in the reaction liquid in the step one is 0.05 mmol/mL-1 mmol/mL. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the mixed solution in the step one is a mixed solution of methanol and water, and the volume ratio of the methanol to the water in the mixed solution is 1 (1-3). The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step two, soaking the foamed nickel in the reaction solution, then reacting for 12-48 h at the temperature of 180-190 ℃, taking out the foamed nickel after the reaction is finished, washing, and drying at the temperature of 60-100 ℃ to obtain the manganese-doped nickel hydroxide nanosheet array. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: adding selenium powder into a sodium borohydride aqueous solution with the concentration of 0.56-1 mmol/L, fully reacting until the solution is clear to obtain a sodium selenide aqueous solution, adding a manganese-doped nickel hydroxide nanosheet array into a reaction kettle containing absolute ethyl alcohol under the nitrogen atmosphere, soaking the reaction kettle in the absolute ethyl alcohol, adding the sodium selenide aqueous solution into the reaction kettle, sealing the reaction kettle, and reacting for 12-24 hours at the temperature of 140-160 ℃ to obtain the selenium-containing nickel-manganese compound. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the molar ratio of the selenium powder to the sodium borohydride in the third step is 1 (2-2.3); the volume ratio of the sodium hydroselenide aqueous solution to the absolute ethyl alcohol in the step two is 1 (10-20). The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and in the fourth step, the selenized nickel-manganese compound is immersed into dilute hydrochloric acid with the concentration of 1 mmol/L-3 mmol/L, the mixture is kept stand for 1 h-3 h, and after the etching is finished, the mixture is taken out, washed and dried to obtain the ultrathin porous nickel selenide nanosheet array. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and in the fourth step, the selenized nickel-manganese compound is immersed into dilute hydrochloric acid with the concentration of 0.2 mmol/L-1 mmol/L, the mixture is kept stand for 3 h-6 h, and the mixture is taken out after etching is finished, washed and dried to obtain the ultrathin porous nickel selenide nanosheet array. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide is carried out according to the following steps:
firstly, preparing a reaction solution:
adding 0.2mmol of nickel nitrate, 0.6mmol of manganese chloride and 1g of hexadecyl trimethyl ammonium bromide into the mixed solution, and fully mixing to obtain a reaction solution;
the mixed solution is a mixed solution of 6mL of methanol and 15mL of water;
secondly, preparing a manganese-doped nickel hydroxide nanosheet array:
soaking foamed nickel in the reaction solution, then reacting for 12 hours at the temperature of 180 ℃, taking out the foamed nickel after the reaction is finished, washing, and drying at the temperature of 60 ℃ to obtain a manganese-doped nickel hydroxide nanosheet array;
the thickness of the foamed nickel is 0.5mm, and the size is 1 multiplied by 3cm2；
Thirdly, selenizing:
adding selenium powder into 3mL of sodium borohydride aqueous solution with the concentration of 0.56mmol/L, fully reacting until the solution is clear to obtain sodium selenide aqueous solution, adding a manganese-doped nickel hydroxide nanosheet array into a reaction kettle containing 30mL of absolute ethyl alcohol under the atmosphere of nitrogen, soaking in the absolute ethyl alcohol, adding the sodium selenide aqueous solution into the reaction kettle, sealing the reaction kettle, and reacting for 12 hours at the temperature of 140 ℃ to obtain a selenium nickel manganese compound;
the molar ratio of the selenium powder to the sodium borohydride is 1: 2.3;
fourthly, acid etching treatment:
immersing the selenized nickel-manganese compound into dilute hydrochloric acid with the concentration of 1mmol/L, standing for 3h, taking out after etching, washing and drying to obtain the ultrathin porous nickel selenide nanosheet array.
Fig. 1 is an SEM photograph of the ultrathin porous nickel selenide nanosheet array prepared in the first embodiment, which is magnified 5000 times, and it is apparent from the SEM photograph that the material prepared in the present embodiment has an ordered three-dimensional nanosheet array structure, and the nanosheet surface has a large number of porous structures due to etching, which can greatly promote electrolyte ion mobility and expose more active sites, and have capacitive properties.
FIG. 2 is an AFM image of an ultrathin porous nickel selenide nanosheet array prepared in example one; FIG. 3 is a graph of the thickness profile corresponding to FIG. 2; as can be seen from the figure, the material prepared by the embodiment is an ultrathin nanosheet structure with uniform thickness, the thickness is about 5nm, and the ultrathin nanosheet can provide more accessible active sites for electrochemical reaction, so that the capacitance performance is far higher than that of a thick plate or a block.
FIG. 4 is a TEM photograph of the ultrathin porous nickel selenide nanosheet array prepared in example one; from the figure, the result of the figure I is also verified, the pore distribution on the nano sheet can be seen from the nanometer scale to hundreds of nanometers, and the hierarchical porous structure also contributes to the improvement of the capacitive performance.
FIG. 5 is a HRTEM photograph of the ultrathin porous nickel selenide nanosheet array prepared in example one; the material is shown to have good crystallinity, the main lattice spacing is 0.27nm, 0.2nm, 0.18nm and 0.26nm, which respectively correspond to NiSe (101), (102), (110) and Makinenite NiSe (021) peaks;
FIG. 6 is an X-ray diffraction pattern of the ultrathin porous nickel selenide nanosheet array prepared in the first example, wherein 1 is a diffraction peak of NiSe, 2 is a diffraction peak of Makinenite NiSe, and 3 is a diffraction peak of metallic nickel; FIG. 6 shows diffraction angles corresponding to the results of the lattice spacing of FIG. 5, which correspond to PDF #02-0829 and PDF #18-0887, respectively. The embodiment comprises the doping of manganese in a precursor and the subsequent two-step etching, the existence of manganese enables the excellent morphology structure of the precursor to be reserved in the subsequent process, and the subsequent etching generates a porous structure beneficial to the capacitance performance.
The capacitance performance of the ultrathin porous nickel selenide nanosheet array prepared in the embodiment is tested by using a Chenghua CHI660E type electrochemical workstation, the ultrathin porous nickel selenide nanosheet array prepared in the embodiment is directly used as a working electrode in a three-electrode system, and a platinum sheet and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode. In the asymmetric test, the ultrathin porous nickel selenide nanosheet array prepared by the embodiment is directly used as a positive electrode, and common activated carbon is used as a negative electrode to perform two-point test. The electrolyte is 3mol/L potassium hydroxide solution. FIG. 7 is a cyclic voltammetry graph of the ultrathin porous nickel selenide nanosheet array prepared in the first example at different scan rates, with 1mV/s, 2mV/s, 3 at 5mV/s, 4 at 10mV/s, and 5 at 20 mV/s; fig. 8 is a constant current charge and discharge curve diagram of the ultrathin porous nickel selenide nanosheet array prepared in the first embodiment at different current densities, where 1 is 3A/g, 2 is 4A/g, 3 is 5A/g, 4 is 6A/g, 5 is 8A/g, and 6 is 10A/g; a pair of redox peaks displayed by the cyclic voltammetry curve shows that the material is a typical pseudocapacitance material and has good charge-discharge reversibility, the area surrounded by the cyclic voltammetry curve is in direct proportion to the capacitance value, and the extremely large area of the cyclic voltammetry curve also shows that the capacitance value of the material is very large. The charge and discharge platform in the constant current charge and discharge result also corresponds to the oxidation reduction peak, the discharge time is about 500s when the current density is 3A/g, and the calculated capacitance value is up to 3546F/g.
Fig. 9 is a cycle stability curve obtained by the ultra-thin porous nickel selenide nanosheet array prepared in the first embodiment under a 5A/g current density continuous charge and discharge test, and it can be seen that after the cycle reaches 5000 times, the capacitance value still remains close to 95%, which proves excellent cycle stability.
Example two: the difference between the present embodiment and the first embodiment is: in the first step, 0.4mmol of nickel nitrate, 0.4mmol of manganese chloride and 1g of hexadecyl trimethyl ammonium bromide are added into the mixed solution and fully mixed to obtain a reaction solution. The rest is the same as the first embodiment.
Example three: the difference between the present embodiment and the first embodiment is: in the first step, 0.6mmol of nickel nitrate, 0.2mmol of manganese chloride and 1g of hexadecyl trimethyl ammonium bromide are added into the mixed solution and fully mixed to obtain a reaction solution. The rest is the same as the first embodiment.
Example four: the difference between the present embodiment and the first embodiment is: the molar ratio of the selenium powder to the sodium borohydride in the third step is 1: 2.1. The rest is the same as the first embodiment.
The capacitance values calculated from the charge and discharge results are shown in fig. 10, where fig. 10 is the variation of mass specific capacitance with current density; 1 is an ultrathin porous nickel selenide nanosheet array prepared in the first example, 2 is an ultrathin porous nickel selenide nanosheet array prepared in the second example, and 3 is a nickel selenide nanosheet array prepared in the third example; the highest capacitance value of the ultrathin porous nickel selenide nanosheet array prepared in the first embodiment is up to 3546F/g (3A/g), and even when the current density reaches 10A/g, the capacitance value is still up to 2533F/g, so that excellent capacitance performance is shown. The maximum capacitance value of the ultrathin porous nickel selenide nanosheet array prepared in the second embodiment reaches 2876F/g (the current density is 3A/g). The maximum capacitance value of the nickel selenide nanosheet array prepared in the third embodiment reaches 2040F/g (current density of 3A/g).
Fig. 11 is an SEM photograph of the ultra-thin porous nickel selenide nanosheet array prepared in example one, magnified 20000 times; fig. 12 is an SEM photograph of the ultra-thin porous nickel selenide nanosheet array prepared in example two, magnified 20000 times; FIG. 13 is an SEM photograph of an array of nickel selenide nanosheets prepared in example three at a magnification of 20000; as can be seen from the figure, compared with the first embodiment, the ultrathin porous nickel selenide nanosheet array prepared in the second embodiment has a significantly smaller pore structure and is thicker. The nickel selenide nanosheet array prepared in example three was thicker and had less pore structure than the nanosheets prepared in example two, and even appeared to have a nearly smooth surface, which resulted in reduced capacitive performance. It is also laterally demonstrated that manganese plays a very important role in the etching of pore structures, and that there are almost no porous structures when the manganese content is reduced to a certain value.
Claims (10)
1. A method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide is characterized in that the method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide is carried out according to the following steps:
firstly, preparing a reaction solution:
adding nickel nitrate, manganese chloride and hexadecyl trimethyl ammonium bromide into the mixed solution, and fully mixing to obtain a reaction solution;
the total concentration of the nickel nitrate and the manganese chloride in the reaction liquid is 0.03 mmol/mL-0.05 mmol/mL; the concentration ratio of the nickel nitrate to the manganese chloride is 1 (1-7); the concentration of hexadecyl trimethyl ammonium bromide in the reaction liquid is 0.05 mmol/mL-1.4 mmol/mL; the mixed solution is a mixed solution of methanol and water, and the volume ratio of the methanol to the water in the mixed solution is 1 (1-6);
secondly, preparing a manganese-doped nickel hydroxide nanosheet array:
soaking foamed nickel in the reaction solution, then reacting for 3-48 h at the temperature of 170-190 ℃, taking out the foamed nickel after the reaction is finished, washing, and drying at the temperature of 40-100 ℃ to obtain a manganese-doped nickel hydroxide nanosheet array;
thirdly, selenizing:
adding selenium powder into a sodium borohydride aqueous solution with the concentration of 0.4 mmol/L-1 mmol/L, fully reacting until the solution is clear to obtain a sodium hydroselenide aqueous solution, adding a manganese-doped nickel hydroxide nanosheet array into a reaction kettle containing absolute ethyl alcohol under the nitrogen atmosphere, soaking the reaction kettle in the absolute ethyl alcohol, adding the sodium hydroselenide aqueous solution into the reaction kettle, sealing the reaction kettle, and reacting for 3-24 hours at the temperature of 140-180 ℃ to obtain a selenium nickel-manganese compound;
the molar ratio of the selenium powder to the sodium borohydride is 1 (2-2.5); the volume ratio of the sodium hydrogen selenide aqueous solution to the absolute ethyl alcohol is 1 (8-20);
fourthly, acid etching treatment:
immersing a selenized nickel-manganese compound into dilute hydrochloric acid with the concentration of 0.2-3 mmol/L, standing for 1-6 h, taking out after etching is finished, washing and drying to obtain an ultrathin porous nickel selenide nanosheet array;
the thickness of the ultrathin porous nickel selenide nanosheet array is 5 nm.
2. The method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein the total concentration of nickel nitrate and manganese chloride in the reaction solution in the first step is from 0.04mmol/mL to 0.05 mmol/mL.
3. The method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein the concentration ratio of nickel nitrate to manganese chloride in the first step is 1 (1-4).
4. The method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein the concentration of cetyltrimethylammonium bromide in the reaction solution in step one is from 0.05mmol/mL to 1 mmol/mL.
5. The method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide as claimed in claim 1, wherein the mixed solution in step one is a mixed solution of methanol and water; the volume ratio of the methanol to the water is 1 (1-3).
6. The method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein selenium powder is added into an aqueous solution of sodium borohydride with a concentration of 0.56mmol/L to 1mmol/L in the third step, and the reaction is carried out fully until the solution is clarified to obtain an aqueous solution of sodium selenide.
7. The method for preparing an ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein in the third step, the manganese-doped nickel hydroxide nanosheet array is immersed in a reaction kettle containing absolute ethanol under a nitrogen atmosphere, and a sodium hydrogen selenide aqueous solution is added, and then the reaction kettle is sealed and reacted at a temperature of 140-160 ℃ for 12-24 h to obtain the nickel manganese selenide compound.
8. The method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein the molar ratio of the selenium powder to the sodium borohydride in the third step is 1 (2-2.3); the volume ratio of the sodium hydrogen selenide aqueous solution to the absolute ethyl alcohol in the step three is 1 (10-20).
9. The method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein in the fourth step, a selenized nickel-manganese compound is immersed in dilute hydrochloric acid with a concentration of 1-3 mmol/L, kept stand for 1-3 h, and taken out after etching is finished, washed and dried to obtain the ultrathin porous nickel selenide nanosheet array.
10. The method for preparing the ultrathin porous nickel selenide nanosheet array by etching manganese-doped nickel hydroxide according to claim 1, wherein in the fourth step, a selenized nickel-manganese compound is immersed in dilute hydrochloric acid with a concentration of 0.2-1 mmol/L, stands for 3-6 h, and is taken out, washed and dried after the etching is finished, so that the ultrathin porous nickel selenide nanosheet array is obtained.
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