CN113845149A - Nano magnesium cobaltate and preparation method and application thereof - Google Patents
Nano magnesium cobaltate and preparation method and application thereof Download PDFInfo
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- CN113845149A CN113845149A CN202110842507.1A CN202110842507A CN113845149A CN 113845149 A CN113845149 A CN 113845149A CN 202110842507 A CN202110842507 A CN 202110842507A CN 113845149 A CN113845149 A CN 113845149A
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- magnesium cobaltate
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- 239000011777 magnesium Substances 0.000 title claims abstract description 145
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 23
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 74
- 229910052759 nickel Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 15
- 239000003990 capacitor Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001429 cobalt ion Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- -1 fluorine ions Chemical class 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 6
- 229910020106 MgCo2O4 Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- LSSAUVYLDMOABJ-UHFFFAOYSA-N [Mg].[Co] Chemical compound [Mg].[Co] LSSAUVYLDMOABJ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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Abstract
The invention provides a nano magnesium cobaltate and a preparation method and application thereof, wherein an XRD (X-ray diffraction) pattern of the magnesium cobaltate has characteristic peaks at diffraction angles 2 theta of 18.96 +/-0.04 degrees, 31.2 +/-0.1 degrees, 36.76 +/-0.1 degrees, 38.46 +/-0.04 degrees, 44.71 +/-0.15 degrees, 55.53 +/-0.1 degrees, 59.22 +/-0.13 degrees, 65.08 +/-0.02 degrees, 68.46 +/-0.11 degrees, 73.94 +/-0.1 degrees, 77.15 +/-0.1 degrees and 78.21 +/-0.5 degrees, the micro morphology of the magnesium cobaltate is a nano needle which is composed of a plurality of nano particles, the length of the nano needle is 1.1-1.54 mu m, the average diameter of the nano needle is 0.08-0.10 mu m, and the nano needle has pores. When the magnesium cobaltate is used as an electrode material and the current density is 25A/g, the rate performance retention rate is 54-63.8%, the current density is 25A/g, the cycle is 10000 cycles, the capacity retention rate is 70.4-98.5%, and the capacity retention rate is high; 10000 cycles of circulation, 1005.3-1449.92F/g of specific discharge capacity and high capacity; so that it can be used for a supercapacitor.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to nano magnesium cobaltate, and a preparation method and application thereof.
Background
Magnesium cobaltate is a metal oxide with high theoretical capacity of 3122F g due to its unique composition and available multiple potential oxidation states-1Is one of the outstanding electrode materials and can be used as the electrode material in the super capacitor. The super capacitor is a novel electronic device between a traditional capacitor and a battery, has high energy density, quick charging/discharging action, environmental friendliness and long cycle life, and also has the characteristics of higher energy density and higher power density than the traditional capacitor and the performance of higher power density than the battery. At present, the super capacitor is put into the life of people for use, small electronic equipment is used in the small super capacitor, and transportation, space shuttles and the like are used in the large super capacitor. No matter which type of equipment needs energy to maintain, however, the low energy density of the super capacitor is still a hot focus at present, and the energy density depends on the electrode material used by the super capacitor, so that the development of a high-performance electrode material for continuously shipping electronic products for a long time is of great significance. However, in practice, magnesium cobaltate is used as an electrode material in a capacitor, and the obtained capacity is not high.
Disclosure of Invention
The invention provides nano magnesium cobaltate, a preparation method and application thereof, and aims to solve the problem of low capacity of magnesium cobaltate in the prior art.
In one aspect, the present invention provides a magnesium cobaltate, wherein an XRD pattern of the magnesium cobaltate has characteristic peaks at diffraction angles 2 θ of 18.96 ± 0.04 °, 31.2 ± 0.1 °, 36.76 ± 0.1 °, 38.46 ± 0.04 °, 44.71 ± 0.15 °, 55.53 ± 0.1 °, 59.22 ± 0.13 °, 65.08 ± 0.02 °, 68.46 ± 0.11 °, 73.94 ± 0.1 °, 77.15 ± 0.1 °, and 78.21 ± 0.5 °, and the magnesium cobaltate is a micro-morphology nanoneedle consisting of a plurality of nanoparticles, the nanoneedle has a length of 1.1 to 1.54 μm, an average diameter of the nanoneedle is 0.08 to 0.10 μm, and the nanoneedle has pores.
In another aspect, the invention provides a method for preparing nano magnesium cobaltate, which comprises the following steps,
mixing a magnesium source, a cobalt source, a precipitator and a structure synthesis agent with water to prepare a mixed solution;
reacting the mixed solution with the pretreated foam nickel at the temperature of 120-130 ℃ for 5-7h to obtain a precursor;
and calcining the precursor to obtain the magnesium cobaltate.
Further, the millimole ratio of the magnesium source, the cobalt source, the precipitating agent and the structure synthesizing agent is 1-10: 2-10: 1-15: 1-5.
Further, the magnesium source is any one of the following: magnesium nitrate, magnesium acetate and magnesium chloride.
Further, the cobalt source is any one of the following: cobalt nitrate, cobalt acetate and cobalt chloride.
Further, the precipitant is any one of the following: urea, oxalic acid and carbonate, wherein the carbonate is any one of the following substances: sodium carbonate, potassium carbonate and calcium carbonate.
Further, the structure-forming agent is ammonium fluoride.
Further, the method may further comprise,
obtaining foam nickel to be treated;
respectively carrying out ultrasonic treatment on the foam nickel to be treated by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water, and drying to obtain pretreated foam nickel; the total ultrasonic time is 15-30min, the drying temperature is 50-80 ℃, and the drying time is 65-75 min.
Furthermore, the heating rate is 4-6 ℃/min, the temperature is 350-.
In a third aspect, the invention also provides an application of the nano magnesium cobaltate, and the nano magnesium cobaltate is applied to a super capacitor as an electrode material.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides nano-magnesium cobaltate and a preparation method and application thereof, wherein the XRD pattern of the magnesium cobaltate has characteristic peaks at diffraction angles 2 theta of 18.96 +/-0.04 degrees, 31.2 +/-0.1 degrees, 36.76 +/-0.1 degrees, 38.46 +/-0.04 degrees, 44.71 +/-0.15 degrees, 55.53 +/-0.1 degrees, 59.22 +/-0.13 degrees, 65.08 +/-0.02 degrees, 68.46 +/-0.11 degrees, 73.94 +/-0.1 degrees, 77.15 +/-0.1 degrees and 78.21 +/-0.5 degrees, and the characteristic peaks of the XRD pattern of the magnesium cobaltate and a cubic spinel phase MgCo phase2O4Standard cards (JCPDS NO.81-0667) were consistent and relatively pure crystals were synthesized, since the resulting sample could be determined to be MgCo2O4Phase, indicating that it is magnesium cobaltate; the nano needle of the magnesium cobaltate in the microscopic appearance is composed of a plurality of nano particles, the length of the nano needle is 1.1-1.54 mu m, the average diameter of the nano needle is 0.08-0.10 mu m, and the nano needle is provided with pores, so that the magnesium cobaltate has an ultrathin structure and a large specific surface area, the contact area of an electrode and dielectric ions is effectively increased, more effective reaction active sites are provided, the contact resistance of the electrode is reduced, the energy density of an electrode material is improved, and the specific capacitance (capacity) of the material is improved. When the magnesium cobaltate is used as an electrode material and the current density is 25A/g, the rate performance retention rate is 54-63.8%, the current density is 25A/g, the cycle is 10000 cycles, the capacity retention rate is 70.4-98.5%, and the capacity retention rate is high; 10000 cycles of circulation, 1005.3-1449.92F/g of specific discharge capacity and high capacity; so that it can be used for a supercapacitor.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a microscopic morphology of magnesium cobaltate provided in example 1 of the present invention;
FIG. 2 is a TEM image of magnesium cobaltate as provided in example 1 of the present invention;
FIG. 3 is a HRTEM image of magnesium cobaltate as provided in example 1 of the present invention;
FIG. 4 is a SAED graph of magnesium cobaltate prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of magnesium cobaltate prepared in example 1 of the present invention;
FIG. 6 is an XRD pattern of magnesium cobaltate prepared in example 1 of the present invention;
FIG. 7 is a Cyclic Voltammetry (CV) curve of magnesium cobaltate prepared in example 1 of the present invention;
FIG. 8 is a constant current charge-discharge (GCD) curve of magnesium cobaltate prepared in example 1 of the present invention;
FIG. 9 is a graph showing the cycle characteristics of magnesium cobaltate prepared in example 1 of the present invention;
FIG. 10 is a graph showing the cycle characteristics of the first 5 cycles and the second 5 cycles of the magnesium cobaltate prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are provided to illustrate the invention, and not to limit the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by an existing method.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
in one aspect, embodiments of the present invention provide a magnesium cobaltate having an XRD pattern with characteristic peaks at diffraction angles 2 θ of 18.96 ± 0.04 °, 31.2 ± 0.1 °, 36.76 ± 0.1 °, 38.46 ± 0.04 °, 44.71 ± 0.15 °, 55.53 ± 0.1 °, 59.22 ± 0.13 °, 65.08 ± 0.02 °, 68.46 ± 0.11 °, 73.94 ± 0.1 °, 77.15 ± 0.1 °, and 78.21 ± 0.5 °, the micro-topographic nanoneedle of the magnesium cobaltate being composed of a plurality of nanoparticles, the nanoneedle having a length of 1.1 to 1.54 μm, the nanoneedle having an average diameter of 0.08 to 0.10 μm, the nanoneedle having pores therein.
Due to the characteristic peak of XRD picture of magnesium cobaltate and the MgCo phase of cubic spinel2O4Standard card (JCPDS NO.81-0667) was consistent with having synthesized relatively pure crystals, since the resulting sample could be determined to be MgCo2O4The magnesium cobaltate provided by the invention has an ultrathin structure due to the fact that the microscopic morphology of the magnesium cobaltate is a nanoneedle, the effective transmission path of electrons or ions can be improved, the contact area of an electrode and dielectric ions is effectively increased, more effective reaction active sites are provided, and therefore, the contact resistance of the electrode is reduced, the energy density of an electrode material is improved, and the specific capacitance (capacity) of the material is improved.
In another aspect, the embodiment of the present invention provides a preparation method of nano magnesium cobaltate, including,
s1, mixing a magnesium source, a cobalt source, a precipitator, a structure synthesis agent and water to prepare a mixed solution;
the function of each raw material in the invention is as follows:
the magnesium source provides raw materials for synthesizing magnesium in the magnesium cobaltate, the cobalt source provides raw materials for providing cobalt in the magnesium cobaltate, and the precipitator has the function of enabling magnesium and cobalt ions to have deposition effect with anions in a solution so as to grow a precursor on the foamed nickel and prepare for subsequent high-temperature oxidation into the magnesium cobaltate; the structural synthesis agent can hydrolyze fluorine ions in solution, generally speaking, the fluorine ions can be selectively adsorbed on each crystal face of magnesium cobaltate, so that the crystallization kinetics of each crystal face is changed, and finally, the material morphology is different.
As an implementation manner of the embodiment of the invention, the millimole ratio of the magnesium source, the cobalt source, the precipitator and the structure synthesis agent is 1-10: 2-10: 1-15: 1-5.
According to MgCo2O4As shown in the chemical formula, the ratio of Mg to Co atoms in the unit cell in the material is 1:2, so that the millimolar ratio of the Mg-Co source added is most preferably 1: 2. Therefore, excessive or insufficient amount of a certain source can cause other impurities (magnesium hydroxide and cobalt hydroxide) to be generated, the synthesis of the magnesium cobaltate crystal is influenced, and the purity of the material is not high.
The precipitator mainly hydrolyzes hydroxide ions to generate precipitation reaction with magnesium and cobalt ions, so that a precursor can be deposited on the foamed nickel, and the precursor can be further oxidized into magnesium cobaltate at high temperature; if the addition amount of the precipitator is too small, magnesium cobalt ions can be insufficiently precipitated, so that the growth of the nanoneedles is insufficient, the nanoneedles are short in length, the pores are reduced, the specific surface area is reduced, and the capacity of the magnesium cobaltate is reduced. On the other hand, the precipitant is excessive, and the hydrolyzed hydroxyl ions are excessive, so that the pH value in the solution is higher, and the solution is strong alkaline, so that the metal conductive substrate foamed nickel is dissolved.
The structural synthesis agent is exemplified by ammonium fluoride, which can hydrolyze F-Wherein the hydrolysis reaction is a reversible reaction, as described above for F-The crystallization kinetics of the crystal face of the magnesium cobaltate can be changed, and the micro-morphology of the material is influenced. If the ammonium fluoride is excessive, magnesium fluoride may be generated in the solution, thereby affecting the purity of the magnesium cobaltate crystal. With OH-The excessive concentration results in magnesium fluoride impurity with low purity.
As an implementation of the embodiment of the present invention, the magnesium source includes, but is not limited to, any one of the following: magnesium nitrate, magnesium acetate and magnesium chloride. The three species can provide magnesium ions.
As an implementation manner of the embodiment of the present invention, the cobalt source includes, but is not limited to, any one of the following: cobalt nitrate, cobalt acetate and cobalt chloride. The three species can provide cobalt ions.
As an implementation manner of the embodiment of the present invention, the precipitating agent is any one of the following: urea, oxalic acid, carbonate selected from sodium carbonate, potassium carbonate or calcium carbonate
Urea, oxalic acid and carbonate can respectively hydrolyze hydroxyl, oxalate and carbonate, and then can generate chemical precipitation reaction with magnesium and cobalt ions to grow a precursor on the foamed nickel, and the precursor is oxidized into magnesium cobaltate at high temperature.
As an implementation of the embodiments of the present invention, the structure-forming agent is ammonium fluoride.
Ammonium fluoride as a structural agent can hydrolyze out fluoride ions, and generally, the fluoride ions can be selectively adsorbed on each crystal face of magnesium cobaltate, so that the crystallization kinetics of each crystal face is changed, and finally, the material morphology is different.
S2, obtaining the foam nickel to be treated;
s3, performing ultrasonic treatment on the foam nickel to be treated by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively, and drying to obtain pretreated foam nickel; the total ultrasonic time is 15-30min, the drying temperature is 50-80 ℃, and the drying time is 65-75 min.
Impurities on the foamed nickel can be removed through ultrasound, and the influence of the impurities on the appearance of the magnesium cobaltate is avoided. The moisture can be removed by drying, so that the moisture-removed foamed nickel is weighed again, and the total mass of the foamed nickel loaded with the magnesium cobaltate after the experiment is prevented from being smaller than that of the foamed nickel before the previous untreated process.
The foamed nickel can be used as a conductive substrate, so that the contact resistance between a precursor and the foamed nickel is reduced, the exposed area of the magnesium cobaltate formed by oxidizing the precursor is increased, the specific capacitance of the magnesium cobaltate is increased, and the problem that the exposed area of the magnesium cobaltate is reduced due to powder accumulation caused by the use of a conductive agent and an adhesive in the traditional process is solved.
Wherein the mass concentration of the dilute hydrochloric acid can be 3mol/L, and the area of the pretreated foamed nickel can be 1 multiplied by 4cm2、2×3cm2、 2×4cm2、1×3cm2、2×2cm2One kind of (1).
S4, reacting the mixed solution with the pretreated nickel foam at the temperature of 120-130 ℃ for 5-7h to obtain a precursor;
the reaction temperature and the reaction time of the mixed solution and the pretreated foamed nickel are controlled, and the magnesium cobaltate with higher crystallization strength and high capacity can be obtained. If the reaction temperature of the mixed solution and the pretreated foamed nickel is too high, although the crystallization strength of the magnesium cobaltate is stronger, the capacity retention rate is higher, the particle size of the magnesium cobaltate nanoparticles is larger, the nanoparticles are easy to cluster, an amorphous irregular shape is formed, and the capacity of the magnesium cobaltate is reduced; on the contrary, the magnesium cobaltate has a shape of nanoneedles and a high capacity, but has a low crystallinity and a low capacity retention rate. The reaction temperature of the mixed solution and the pretreated nickel foam is preferably 120 ℃.
The reaction time of the mixed solution and the pretreated nickel foam is too long, so that magnesium ions and cobalt ions excessively grow, the length of the nano needles is too long, the nano needles are very compact, and the distance between different nano needles is reduced, so that the specific surface area of the magnesium cobaltate is reduced, the electrolyte passing rate is low, the generated electrons are few, and the capacity is reduced; the reaction time is too short, so that the growth of magnesium ions and cobalt ions is insufficient, the number of nanowires is small and short, the synthesis of material crystals is weak, and the morphology is not fully grown, so that the specific surface area of magnesium cobaltate is small, electrons generated when an electrolyte passes through the magnesium cobaltate are few, and the capacity is reduced.
And S5, calcining the precursor to obtain the nano magnesium cobaltate.
As an implementation manner of the embodiment of the invention, in the calcination process, the temperature rise rate is 4-6 ℃/min, the temperature is 350-.
On one hand, the dried moisture and the contained impurities can be further removed through calcination, and on the other hand, the precursor is oxidized into the porous and nanoneedle-structured magnesium cobaltate by utilizing high temperature and air in the environment.
The temperature rise rate is mainly used for controlling the calcination time length so as to improve the experimental efficiency.
Under the same time, the calcination temperature is too high or too low, on one hand, the material morphology is clustered and stacked, and gaps and pores are less. On the other hand, the crystallinity of the material is good, and the expansion and contraction of crystal grains of the material are limited to influence the diffusion of magnesium cobalt ions, so that the charge transfer resistance is increased, and the specific capacitance of the magnesium cobalt is reduced. Meanwhile, the calcining temperature is too low, the chemical reaction is insufficient, and the precursor is not easy to decompose, so that the appearance and the structure of the magnesium cobaltate are not fully embodied.
The calcination time is too short, and the oxidation reaction is not sufficient, so that the appearance and the structure of the magnesium cobaltate are not fully embodied.
In another aspect, an embodiment of the present invention provides an application of nano magnesium cobaltate, in which magnesium cobaltate is applied to a supercapacitor as an electrode material.
The preparation method and application of the nano magnesium cobaltate of the present invention will be described in detail below with reference to examples, comparative examples and experimental data.
Example 1
1. 0.2564g of magnesium nitrate (1mmol), 0.5820g of cobalt nitrate (2mmol), 0.3g of urea (5mmol) and 0.074g of ammonium fluoride (2mmol) were weighed out and dissolved in 50ml of deionized water, followed by stirring for 1 hour to obtain a uniformly mixed solution.
2. Foamed nickel (1X 4 cm)2) Respectively carrying out ultrasonic treatment for 15 minutes by using 3mol/L diluted hydrochloric acid, acetone, absolute ethyl alcohol and deionized water, and drying at the temperature of 50 ℃ for 70 minutes.
3. And (3) transferring the mixed solution obtained in the step (1) and the foamed nickel obtained in the step (2) into a 100ml reaction kettle, carrying out hydrothermal treatment for 6 hours at 120 ℃, naturally cooling to room temperature, washing with absolute ethyl alcohol and deionized water for 3 times respectively, and drying for 5 hours at 60 ℃ to obtain the magnesium cobaltate precursor.
4. And (3) heating the precursor obtained in the step (3) to 350 ℃, wherein the heating rate is 5 ℃/min, and calcining for 2 hours in the air atmosphere to obtain the foamed nickel with the black substances, namely the required magnesium cobaltate.
Example 2
1. 0.322g of magnesium acetate (1.5mmol), 0.53g of cobalt acetate (3mmol), 0.54g of oxalic acid (6mmol) and 0.056g of ammonium fluoride (1.5mmol) were dissolved in 50ml of deionized water and stirred for 1 hour to obtain a uniformly mixed solution.
2. Foamed nickel (2X 3 cm)2) Respectively carrying out ultrasonic treatment for 20 minutes by using 3mol/L diluted hydrochloric acid, acetone, absolute ethyl alcohol and deionized water, and drying at the temperature of 60 ℃ for 65 minutes.
3. And (3) transferring the mixed solution obtained in the step (1) and the foamed nickel obtained in the step (2) into a 100ml reaction kettle, carrying out hydrothermal treatment for 5 hours at 125 ℃, naturally cooling to room temperature, washing with absolute ethyl alcohol and deionized water for 4 times respectively, and drying for 5 hours at 60 ℃ to obtain the magnesium cobaltate precursor.
4. And (3) heating the precursor obtained in the step (3) to 380 ℃, wherein the heating rate is 6 ℃/min, and calcining for 2.5 hours in the air atmosphere to obtain the foamed nickel with black substances, namely the required magnesium cobaltate.
Example 3
Embodiment 3 provides a nano magnesium cobaltate and a preparation method and application thereof, wherein the method specifically comprises the following steps:
1. 0.19g of magnesium chloride (2mmol), 0.95g of cobalt chloride (4mmol), 1.6g of sodium carbonate (15mmol) and 0.037g of ammonium fluoride (1mmol) were weighed out and dissolved in 50ml of deionized water, and stirred for 1 hour to obtain a uniformly mixed solution.
2. Foamed nickel (2X 4 cm)2) Respectively carrying out ultrasonic treatment for 25 minutes by using 3mol/L dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water, and drying at the temperature of 70 ℃ for 68 minutes.
3. And (3) transferring the mixed solution obtained in the step (1) and the foamed nickel obtained in the step (2) into a 100ml reaction kettle, carrying out hydrothermal treatment for 6.5 hours at 128 ℃, naturally cooling to room temperature, washing with absolute ethyl alcohol and deionized water for 2 times respectively, and drying for 5 hours at 60 ℃ to obtain the magnesium cobaltate precursor.
4. And (3) heating the precursor obtained in the step (3) to 385 ℃, wherein the heating rate is 5 ℃/min, and calcining for 3 hours in the air atmosphere to obtain the foamed nickel with the black substances, namely the required magnesium cobaltate.
Comparative example 1
Comparative example 1 reference example 1, comparative example 1 and example 1 were different in that the hydrothermal treatment temperature was 100 ℃ and the hydrothermal treatment time was 4 hours in step 3, and the rest was the same as example 1.
Comparative example 2
Comparative example 2 referring to example 1, comparative example 2 differs from example 1 in that the hydrothermal treatment temperature in step 3 is 150 ℃ and the hydrothermal treatment time is 9 hours, and the rest is the same as example 1.
The magnesium cobaltate prepared in example 1 was observed by scanning electron microscopy (sem) and characterized by Transmission Electron Microscopy (TEM) using an X-ray diffractometer (XRD) as shown in fig. 1-10. The magnesium cobaltate prepared in the examples 1 to 3 is subjected to electrochemical performance tests, which specifically comprise the following steps: the electrochemical performance test is carried out by adopting a traditional three-electrode system, foam nickel coated by a magnesium cobaltate material is directly used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a platinum sheet is used as a counter electrode; the electrolyte solution was 2mol/L KOH. The scanning voltage range is 0-0.5V, and the scanning speed is 10 mV/s. The charge-discharge voltage range is 0-0.5V, and the current density is 2A/g and 25A/g. The voltage range of the cycle performance was 0 to 0.5V, and 10000 cycles were carried out at a current density of 25A/g, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the specific capacitance and cycle performance data of the material are relatively considerable, and the material is suitable for being used as an electrode material of a super capacitor. The rate performance retention rates of the magnesium cobaltate used as the electrode material in the embodiments 1-3 are 63.8%, 54% and 62% when the current density is 2A/g and 25A/g, respectively, the current density is 25A/g and the cycle is 10000 circles, the capacity retention rates are 98.5%, 84.8% and 70.4%, respectively, the original capacity of the magnesium cobaltate electrode material in the embodiments 1-3 is maintained, and the capacity retention rate is high; the discharge specific capacity of 10000 cycles of cycle test is 1005.3-1449.92F/g, and the capacity is high.
In comparative example 1, when the test was performed at a large current of 25A/g, the electrode material was in contact with the electrolyte faster, and the utilization rate of magnesium cobaltate was not high, resulting in failure to detect the capacity of magnesium cobaltate, and vice versa, because the magnesium cobaltate prepared in comparative example 2 formed poor micro-morphology resulting in low capacity.
The rate performance retention rate of the magnesium cobaltate used as the electrode material in the comparative example 2 is 44.16% when the current density is 2A/g and 25A/g, the current density is 25A/g, the circulation is 10000 circles, and the capacity retention rate is 48%.
Fig. 1 is a microscopic morphology of magnesium cobaltate provided in embodiment 1 of the present invention, and as can be seen from fig. 1, the magnesium cobaltate provided in the present invention is composed of nanoneedles, has an ultra-thin structure, can improve an effective transmission path of electrons or ions, effectively increases a contact area between an electrode and dielectric ions, and provides more effective reactive sites, thereby reducing a contact resistance of the electrode, and increasing an energy density of an electrode material, so that the electrode material has a high capacity retention rate;
FIG. 2 is a TEM image of magnesium cobaltate provided in example 1 of the present invention, and it can be seen from FIG. 2 that the magnesium cobaltate nanowire has an ultra-thin and porous structure; the black part on the nano wire represents that atoms are arranged tightly, the pores on the nano wire are few, and the black part is less than the semitransparent part; the semitransparent part on the nanowire shows that the atomic arrangement is loose and thin, a large amount of pores are distributed on the nanowire, the specific surface area is large, electrolyte filtration is facilitated, the redox reaction is sufficient, more electrons are generated, the capacity is high, the discharge time is long, the working voltage window of the capacitor is wide, and the application range is wide;
FIG. 3 is an HRTEM image of magnesium cobaltate provided in example 1 of the present invention, and as can be seen from FIG. 3, the interplanar spacings of 0.468, 0.281, 0.243nm and 0.183nm are respectively designated as magnesium cobaltate crystal planes (111), (220), (311) and (331), indicating that the synthesized magnesium cobaltate crystal is obtained;
FIG. 4 is a SAED graph of magnesium cobaltate provided in example 1 of the present invention, and it can be seen from FIG. 4 that there are many clear and bright diffraction spots, which on the one hand illustrate the material having higher crystallization strength and on the other hand show that the material possesses a porous structure, which is consistent with the results characterized in FIG. 2;
FIG. 5 is a scanning electron microscope image of magnesium cobaltate prepared in example 1 of the present invention, and it can be seen from FIG. 5 that the magnesium cobaltate contains Mg, Co and O elements;
FIG. 6 is an XRD pattern of magnesium cobaltate prepared in example 1 of the present invention, and as can be seen from FIG. 6, the XRD pattern of the magnesium cobaltate has characteristic peaks at diffraction angles 2 θ of 18.96. + -. 0.04 °, 31.2. + -. 0.1 °, 36.76. + -. 0.1 °, 38.46. + -. 0.04 °, 44.71. + -. 0.15 °, 55.53. + -. 0.1 °, 59.22. + -. 0.13 °, 65.08. + -. 0.02 °, 68.46. + -. 0.11 °, 73.94. + -. 0.1 °, 77.15. + -. 0.1 °, and 78.21. + -. 0.5 °, MgCo and cubic spinel phases2O4Standard card (JCPDS NO.81-0667) was consistent and relatively pure crystals had been synthesized;
FIG. 7 is a Cyclic Voltammetry (CV) curve of magnesium cobaltate prepared in example 1 of the present invention, and it can be seen from FIG. 7 that a pair of significant redox peaks appear in the curve within a voltage window of 0-0.5V, indicating that the magnesium cobaltate undergoes a Faraday redox reaction in the electrolyte;
fig. 8 is a constant current charge and discharge (GCD) curve of magnesium cobaltate prepared in example 1 of the present invention, and it can be seen from fig. 8 that the charge time is substantially equal to the discharge time, indicating that the magnesium cobaltate material has good reversibility. At the same time, the GCD curve shows a potential plateau, indicating that the material possesses redox activity, which is consistent with the results of the analysis in fig. 7;
FIG. 9 is a cycle characteristic diagram of magnesium cobaltate prepared in example 1 of the present invention, and it can be seen from FIG. 9 that the specific capacitance of nano-magnesium cobaltate changes from 736C/g to 724.96C/g after 10000 cycles, and the capacity retention rate is high;
fig. 10 is a graph showing the cycle characteristics of the magnesium cobaltate prepared in example 1 compared with the first 5 cycles and the last 5 cycles, and as can be seen from fig. 9, the first 5 cycles and the last 5 cycles are not greatly different, indicating that the material has long-term electrochemical cycle stability.
The invention provides nano magnesium cobaltate and a preparation method and application thereof, wherein an XRD (X-ray diffraction) pattern of the magnesium cobaltate has characteristic peaks at diffraction angles 2 theta of 18.96 degrees, 31.2 degrees, 36.76 degrees, 38.46 degrees, 44.71 degrees, 55.53 degrees, 59.22 degrees, 65.08 degrees, 68.46 degrees, 73.94 degrees, 77.15 degrees and 78.21 degrees, and the characteristic peaks of an XRD (X-ray diffraction) picture of the magnesium cobaltate and a cubic spinel phase MgCo2O4Standard card (JCPDS NO.81-0667) was consistent with having synthesized relatively pure crystals, since the resulting sample could be determined to be MgCo2O4Phase, indicating that it is magnesium cobaltate; the micro-morphology of the magnesium cobaltate is a nano needle, the length of the nano needle is 1.1-1.54 mu m, the nano needle is formed by stacking nano particles, the nano needle is provided with pores and is of an ultrathin structure, an effective transmission path of electrons or ions can be improved, the contact area of an electrode and dielectric ions is effectively increased, more effective reaction active sites are provided, and therefore the contact resistance of the electrode is reduced, the energy density of an electrode material is improved, the capacity of the electrode material is high, and the capacity retention rate is high. When the magnesium cobaltate is used as an electrode material, the rate of retention of the multiplying power performance is 54-63.8% when the current density is 25A/g, the current density is 25A/g and 10000 cycles are circulated, the capacity retention rate is 70.4-98.5%, and the capacity retention rate is high, so that the magnesium cobaltate can be used for a super capacitor; 10000 cycles of circulation, 1005.3-1449.92F/g of specific discharge capacity and high capacity. The synthesis method of the magnesium cobaltate provided by the invention is simple and in place in one step, and the preparation process technology of the high-performance material is simplified.
Finally, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A magnesium cobaltate nanoparticle, characterized in that the XRD pattern of the magnesium cobaltate has characteristic peaks at diffraction angles 2 theta of 18.96 +/-0.04 degrees, 31.2 +/-0.1 degrees, 36.76 +/-0.1 degrees, 38.46 +/-0.04 degrees, 44.71 +/-0.15 degrees, 55.53 +/-0.1 degrees, 59.22 +/-0.13 degrees, 65.08 +/-0.02 degrees, 68.46 +/-0.11 degrees, 73.94 +/-0.1 degrees, 77.15 +/-0.1 degrees and 78.21 +/-0.5 degrees, the micro-morphology of the magnesium cobaltate is a nanoneedle, the nanoneedle consists of a plurality of nanoparticles, the length of the nanoneedle is 1.1-1.54 mu m, the average diameter of the nanoneedle is 0.08-0.10 mu m, and the nanoneedle has pores.
2. The method according to claim 1, wherein the method comprises the steps of,
mixing a magnesium source, a cobalt source, a precipitator and a structure synthesis agent with water to prepare a mixed solution;
reacting the mixed solution with the pretreated foam nickel at the temperature of 120-130 ℃ for 5-7h to obtain a precursor;
and calcining the precursor to obtain the magnesium cobaltate.
3. The method for preparing nano magnesium cobaltate according to claim 2, wherein the millimolar ratio of the magnesium source, the cobalt source, the precipitant and the structure forming agent is 1-10: 2-10: 1-15: 1-5.
4. The method for preparing nano magnesium cobaltate according to claim 2, wherein the magnesium source is any one of the following: magnesium nitrate, magnesium acetate and magnesium chloride.
5. The method for preparing nano magnesium cobaltate according to claim 2, wherein the cobalt source is any one of the following: cobalt nitrate, cobalt acetate and cobalt chloride.
6. The method for preparing nano magnesium cobaltate according to claim 2, wherein the precipitant is any one of the following: urea, oxalic acid and carbonate, wherein the carbonate is any one of the following substances: sodium carbonate, potassium carbonate and calcium carbonate.
7. The method according to claim 2, wherein the structure-forming agent is ammonium fluoride.
8. The method for preparing nano magnesium cobaltate according to claim 2, further comprising the steps of,
obtaining foam nickel to be treated;
respectively carrying out ultrasonic treatment on the foam nickel to be treated by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water, and drying to obtain pretreated foam nickel; the total ultrasonic time is 15-30min, the drying temperature is 50-80 ℃, and the drying time is 65-75 min.
9. The method for preparing nano magnesium cobaltate as claimed in claim 2, wherein the temperature rise rate is 4-6 ℃/min, the temperature is 350-400 ℃ and the time is 2-3h during the calcination process.
10. The use of nano magnesium cobaltate according to claim 1, wherein the magnesium cobaltate is used as an electrode material in a supercapacitor.
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Application publication date: 20211228 |