CN114121495A - Nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite and preparation method thereof - Google Patents
Nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 7
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 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 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000008098 formaldehyde solution Substances 0.000 claims description 7
- 102000020897 Formins Human genes 0.000 claims description 6
- 108091022623 Formins Proteins 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
The invention discloses a nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material and a preparation method thereof. The hollow mesoporous carbon sphere is used as a micro nano reactor, and the limited-area growth of the nickel-cobalt-manganese hydroxide nanosheets on the inner surface and the outer surface of the hollow mesoporous carbon sphere is regulated and controlled by regulating and controlling the content of the hollow mesoporous carbon sphere. The hierarchical spherical nano structure enables the electrode material to have higher active specific surface area and shorter ion transmission path, and maintains better structural stability in the charging and discharging process; the nickel-cobalt-manganese hydroxide nanosheets grow inside and outside the carbon spheres, the stacking density of the active material can be improved, additional reactive sites are provided, and the current density is 1A g‑1When the specific capacitance reaches 1455.2 Ccm‑3At a current density of up to 20A g‑1The specific capacitance of the capacitor is still as high as 1005.0 Ccm‑3Showing better multiplying power; at a current density of 10A g‑1The cycle performance of the material is tested under the condition, the capacity retention rate reaches 86.8% after 5000 circles, and the material has good cycle stability.
Description
Technical Field
The invention relates to a nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material and a preparation method thereof, and belongs to the field of nano material preparation.
Background
In recent years, due to rapid climate change and exhaustion of fossil energy, more researches on the production of green energy and advanced energy storage systems have been conducted. Among many energy storage devices, a super capacitor is a new generation of electrochemical energy storage device due to its characteristics of high power density, fast charge and discharge, and long cycle life, and the electrode material is the key to determine the performance of the super capacitor.
The transition metal hydroxide has the characteristics of rich oxidation-reduction reaction sites, adjustable structure, low cost, environmental friendliness and the like. Compared with single metal hydroxide, the nickel-cobalt-manganese ternary hydroxide has high theoretical capacity, rich chemical valence and better chemical stability. However, the low conductivity and large volume expansion characteristic of the nickel-cobalt-manganese hydroxide are easy to reduce the overall electrochemical performance, and the nickel-cobalt-manganese hydroxide can be effectively compounded with a carbon material to solve the problems. ZHou et al coated small size ultrathin nickel hydroxide nanosheets [ Y. Fu, Y. ZHou, Q. Peng, C. Yu, Z. Wu, J. Sun, J. Zhu, X. Wang, Hollow mesoporous carbon spheres endrawn by small-sized and amorphous hydrophilic nanoparticles for high-performance hydrophilic nanoparticles ] on the surface of Hollow mesoporous carbon spheres, J. Power Sources 402 (2018) 43-52.]. Liu et al loaded Co on nitrogen-doped carbon hollow sphere3O4Nanoparticles [ T. Liu, L. Zhang, W. You, J. Yu, Core-shell nitro-bonded carbon hold Spheres/Co3O4 nanosheets as advanced electrode for high-performance supercapacitor, Small 14 (2018) 1702407.]. In the composite material prepared by the method, the active substance is only loaded on the outer surface of the hollow carbon sphere, and the inner surface is not fully utilized, so that the overall electrochemical performance of the composite material is limited.
Disclosure of Invention
The invention aims to provide a nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows: according to the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite, nickel-cobalt-manganese hydroxide nanosheets grow in a limited area on the inner surface and the outer surface of a hollow mesoporous carbon sphere.
The preparation method of the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite comprises the following steps of, by using hollow mesoporous carbon spheres as a micro-nano reactor, preferentially nucleating the nickel-cobalt-manganese hydroxide inside to grow, and then growing on the outer surfaces of the hollow mesoporous carbon spheres:
firstly, putting a nitrate mixed solution of nickel, cobalt and manganese into a hollow mesoporous carbon sphere precursor solution, and stirring for a period of time;
and step two, adding a urotropine solution into the solution obtained in the step one, reacting for a period of time at a constant temperature, cleaning the obtained product, and drying to obtain the composite material.
Preferably, the hollow mesoporous carbon sphere precursor solution is prepared by the following steps:
(1) adding tetraethyl orthosilicate into a mixed solution containing absolute ethyl alcohol, deionized water and ammonia water, stirring in a constant-temperature water bath at the temperature of 20-30 ℃ for a period of time, adding resorcinol, continuing stirring, adding a formaldehyde solution, and stirring for more than 24 hours;
(2) cleaning the precipitate obtained in the step (1), drying, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere-1Temperature rise ofRaising the speed to 700 +/-10 ℃ and reacting for 5 hours at constant temperature;
(3) and (3) etching the product obtained in the step (2) by adopting a hydrofluoric acid solution, cleaning, drying, and ultrasonically dispersing uniformly in deionized water to obtain a hollow mesoporous carbon sphere precursor solution.
Preferably, the molar ratio of nickel, cobalt and manganese in the nitrate mixed solution of nickel, cobalt and manganese is 1: 1: 1.
preferably, the mass ratio of the hollow mesoporous carbon spheres to the nickel nitrate in the nitrate mixed solution of nickel, cobalt and manganese is 0.03-0.17.
Preferably, the molar ratio of the urotropine to the metal ions in the nitrate mixed solution of nickel, cobalt and manganese is 1.67: 1.
preferably, in the first step, the stirring time is 12 hours or more.
Preferably, in the second step, the reaction is carried out at a constant temperature of 80 +/-5 ℃ for 5-7 hours.
Compared with the prior art, the invention has the advantages that: (1) the nano composite material of the nickel-cobalt-manganese hydroxide nanosheets growing inside and outside the hollow mesoporous carbon spheres can be accurately obtained by regulating the content of the hollow mesoporous carbon spheres. (2) The hollow composite structure can enable the electrode material to have higher active specific surface area and shorter ion transmission path, and maintain better structural stability in the charging and discharging process; the nickel-cobalt-manganese hydroxide nanosheets grow inside and outside, so that the bulk density of the active material can be further improved, and additional reactive sites are provided. (3) The nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material is used as an electrode material of a supercapacitor, and the current density is 1A g-1When the specific capacitance reaches 779C g-1At a current density of up to 20A g-1The specific capacitance is still as high as 538C g-1And the better multiplying power is shown. At a current density of 10A g-1The cycle performance of the material is tested under the condition, the capacity retention rate reaches 86.8% after 5000 circles, and the material has good cycle stability.
Drawings
Fig. 1 is a schematic view of a synthesis method according to the present invention and TEM images of hollow mesoporous carbon spheres and examples 1 to 4 according to the present invention, (a) a schematic view of a synthesis method, (b) hollow mesoporous carbon spheres, and (c-f) nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposites having different carbon contents.
FIG. 2 is a graph showing the morphology of the nanocomposites prepared in example 2 of the present invention and comparative examples 1-2. (a, b) and (c) are TEM and FESEM images of pure nickel cobalt manganese hydroxide, respectively; (d, e) and (f) are TEM and FESEM images of the hollow mesoporous carbon sphere @ nickel cobalt manganese hydroxide, respectively; (g, j), (h, l) and (i) are TEM, HAADF-STEM and FESEM images of Ni-Co-Mn hydroxide @ hollow mesoporous carbon spheres, respectively; (k) an HRTEM image of nickel cobalt manganese hydroxide @ hollow mesoporous carbon spheres.
Fig. 3 is XRD diffraction patterns of the hollow mesoporous carbon spheres, pure nickel cobalt manganese hydroxide, hollow mesoporous carbon spheres @ nickel cobalt manganese hydroxide and nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposites prepared in examples 1-4 and comparative examples 1-2 of the present invention with different carbon contents.
Fig. 4 shows BJH pore size distribution curves (a) and nitrogen adsorption desorption isotherms (b) of the hollow mesoporous carbon spheres, pure nickel cobalt manganese hydroxide, hollow mesoporous carbon spheres @ nickel cobalt manganese hydroxide and nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposites prepared in example 2 of the present invention and comparative examples 1-2.
Fig. 5 is a charge-discharge curve (a) and a rate performance graph (b) of pure nickel cobalt manganese hydroxide, hollow mesoporous carbon spheres @ nickel cobalt manganese hydroxide and nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposites with different carbon contents prepared in examples 1-4 and comparative examples 1-2 of the present invention.
Fig. 6 is a graph comparing the volumetric specific capacities of the hollow mesoporous carbon sphere @ nickel cobalt manganese hydroxide and the nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite prepared in example 2 and comparative example 2 according to the present invention.
Fig. 7 is a graph showing the cycle stability performance of the pure nickel cobalt manganese hydroxide, the hollow mesoporous carbon sphere @ nickel cobalt manganese hydroxide and the nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite prepared in example 1 and comparative examples 1-2 of the present invention.
Detailed Description
FIG. 1 (a) is thisThe synthesis method of the invention is shown schematically. Firstly, silicon dioxide @ silicon dioxide/resorcinol formaldehyde resin core-shell nanospheres with uniform size are formed in a mixed solution system containing tetraethyl orthosilicate, and are carbonized and etched in an inert gas atmosphere to obtain hollow mesoporous carbon spheres. In a mixed solution system of carbon spheres and metal ions, the inner and outer surfaces of the hollow mesoporous carbon spheres contain rich oxygen-containing functional groups, and the metal ions are adsorbed on the inner and outer surfaces of the carbon spheres under the electrostatic action generated by the oxygen-containing functional groups; meanwhile, the hollow mesoporous carbon spheres are made of SiO2The inner surface of the hollow mesoporous carbon sphere is rougher and has more oxygen-containing functional groups, so that the adsorption of metal ions is facilitated, the preferential nucleation growth of the nickel-cobalt-manganese hydroxide nanosheets inside the hollow mesoporous carbon sphere is caused, and finally, nanoflowers assembled by the nickel-cobalt-manganese hydroxide nanosheets with the size of about 340 nm are packaged inside the hollow mesoporous carbon sphere along with the reaction, and the thin nickel-cobalt-manganese hydroxide nanosheets are uniformly wrapped on the outer surface of the hollow mesoporous carbon sphere.
The nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite prepared by the method has excellent electrochemical performance as a supercapacitor electrode material, and is mainly due to the unique nanostructure: the hollow mesoporous carbon sphere is used as a micro nano reactor, so that the nickel-cobalt-manganese hydroxide nanosheets grow in a limited area on the inner surface and the outer surface of the hollow mesoporous carbon sphere, the hollow composite structure can enable the electrode material to have a high active specific surface area and a short ion transmission path, and good structural stability is maintained in the charging and discharging process; the nickel-cobalt-manganese hydroxide nanosheets grow inside and outside, so that the stacking density of the active material can be further improved, additional reactive active sites are provided, and good electrochemical performance is shown.
The nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite is prepared by the following steps:
step one, adding tetraethyl orthosilicate into a mixed solution containing absolute ethyl alcohol, deionized water and ammonia water, stirring in a constant-temperature water bath at 25 ℃ for 20 min, adding resorcinol, continuing stirring for 10 min, adding a formaldehyde solution, and stirring for more than 24 h;
the second step, the precipitate obtained in the first step is dried after being cleanedIn a nitrogen atmosphere at 2 ℃ for min-1The temperature is raised to 700 +/-10 ℃ at the temperature raising rate, and the reaction is carried out for 5 hours;
step three, etching the product obtained in the step two for more than 2 times by adopting a hydrofluoric acid solution with the mass fraction of 10%;
fourthly, ultrasonically dispersing 20-100 mg of the hollow mesoporous carbon spheres obtained in the third step in 30 mL of deionized water for 60 min;
fifthly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 30 mL of deionized water;
sixthly, mixing the solution obtained in the fourth step with the solution obtained in the fifth step, and stirring for more than 12 hours;
seventhly, adding 10 mL of urotropine solution with the molar concentration of 1M into the solution obtained in the sixth step, and reacting for 6 hours at the constant temperature of 80 ℃;
and eighth step, cleaning and drying the product obtained in the seventh step to obtain the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material.
Example 1:
step one, adding 27.7 mL tetraethyl orthosilicate into a solution containing 560 mL absolute ethyl alcohol, 80 mL deionized water and 24 mL strong ammonia water, stirring in a constant-temperature water bath at 25 ℃ for 20 min, adding resorcinol, stirring for 10 min, adding a formaldehyde solution, and stirring for more than 24 h;
step two, cleaning and drying the precipitate obtained in the step one, and then drying the precipitate at the temperature of 2 ℃ for min in nitrogen atmosphere-1The temperature rising rate is increased to 700 +/-10 ℃, and the reaction is carried out for 5 hours at constant temperature;
step three, etching the product obtained in the step two for more than 2 times by adopting a hydrofluoric acid solution with the mass fraction of 10%;
fourthly, the product obtained in the third step is dried after being cleaned, and 20 mg of the product is taken to be ultrasonically dispersed in 30 mL of deionized water for 60 min;
fifthly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 30 mL of deionized water;
sixthly, mixing the solution obtained in the fourth step with the solution obtained in the fifth step, and stirring for more than 12 hours;
seventhly, adding 10 mL of urotropine solution with the molar concentration of 1M into the solution obtained in the sixth step, and reacting for 6 hours at the constant temperature of 80 ℃;
and eighth step, cleaning and drying the product obtained in the seventh step to obtain the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material.
Example 2:
step one, adding 27.7 mL tetraethyl orthosilicate into a solution containing 560 mL absolute ethyl alcohol, 80 mL deionized water and 24 mL strong ammonia water, stirring in a constant-temperature water bath at 25 ℃ for 20 min, adding resorcinol, stirring for 10 min, adding a formaldehyde solution, and stirring for more than 24 h;
step two, cleaning and drying the precipitate obtained in the step one, and then drying the precipitate at the temperature of 2 ℃ for min in nitrogen atmosphere-1The temperature rising rate is increased to 700 +/-10 ℃, and the reaction is carried out for 5 hours at constant temperature;
step three, etching the product obtained in the step two for more than 2 times by adopting a hydrofluoric acid solution with the mass fraction of 10%;
fourthly, the product obtained in the third step is dried after being cleaned, and 40 mg of the product is taken to be ultrasonically dispersed in 30 mL of deionized water for 60 min;
fifthly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 30 mL of deionized water;
sixthly, mixing the solution obtained in the fourth step with the solution obtained in the fifth step, and stirring for more than 12 hours;
seventhly, adding 10 mL of urotropine solution with the molar concentration of 1M into the solution obtained in the sixth step, and reacting for 6 hours at the constant temperature of 80 ℃;
and eighth step, cleaning and drying the product obtained in the seventh step to obtain the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material.
Example 3:
step one, adding 27.7 mL tetraethyl orthosilicate into a solution containing 560 mL absolute ethyl alcohol, 80 mL deionized water and 24 mL strong ammonia water, stirring in a constant-temperature water bath at 25 ℃ for 20 min, adding resorcinol, stirring for 10 min, adding a formaldehyde solution, and stirring for more than 24 h;
step two, cleaning and drying the precipitate obtained in the step one, and then drying the precipitate at the temperature of 2 ℃ for min in nitrogen atmosphere-1The temperature rising rate is increased to 700 +/-10 ℃, and the reaction is carried out for 5 hours at constant temperature;
step three, etching the product obtained in the step two for more than 2 times by adopting a hydrofluoric acid solution with the mass fraction of 10%;
fourthly, the product obtained in the third step is dried after being cleaned, and 60 mg of the product is taken to be ultrasonically dispersed in 30 mL of deionized water for 60 min;
fifthly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 30 mL of deionized water;
sixthly, mixing the solution obtained in the fourth step with the solution obtained in the fifth step, and stirring for more than 12 hours;
seventhly, adding 10 mL of urotropine solution with the molar concentration of 1M into the solution obtained in the sixth step, and reacting for 6 hours at the constant temperature of 80 ℃;
and eighth step, cleaning and drying the product obtained in the seventh step to obtain the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material.
Example 4:
step one, adding 27.7 mL tetraethyl orthosilicate into a solution containing 560 mL absolute ethyl alcohol, 80 mL deionized water and 24 mL strong ammonia water, stirring in a constant-temperature water bath at 25 ℃ for 20 min, adding resorcinol, stirring for 10 min, adding a formaldehyde solution, and stirring for more than 24 h;
step two, cleaning and drying the precipitate obtained in the step one, and then drying the precipitate at the temperature of 2 ℃ for min in nitrogen atmosphere-1The temperature rising rate is increased to 700 +/-10 ℃, and the reaction is carried out for 5 hours at constant temperature;
step three, etching the product obtained in the step two for more than 2 times by adopting a hydrofluoric acid solution with the mass fraction of 10%;
fourthly, cleaning and drying the product obtained in the third step, and ultrasonically dispersing 100 mg of the product in 30 mL of deionized water for 60 min;
fifthly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 30 mL of deionized water;
sixthly, mixing the solution obtained in the fourth step with the solution obtained in the fifth step, and stirring for more than 12 hours;
seventhly, adding 10 mL of urotropine solution with the molar concentration of 1M into the solution obtained in the sixth step, and reacting for 6 hours at the constant temperature of 80 ℃;
and eighth step, cleaning and drying the product obtained in the seventh step to obtain the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material.
Comparative example 1:
firstly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 40 mL of deionized water;
secondly, adding 30 mL of aqueous solution containing 10 mmol of urotropine into the solution obtained in the first step, and reacting for 6 h at the constant temperature of 80 ℃;
and step three, cleaning and drying the product obtained in the step two to obtain the pure nickel-cobalt-manganese hydroxide.
Comparative example 2:
step one, uniformly dispersing 360 mg of silicon dioxide @ silicon dioxide/resorcinol formaldehyde resin in 30 mL of deionized water;
secondly, respectively stirring and dissolving 0.593 g of nickel nitrate, 0.5879 g of cobalt nitrate and 0.7158 g of manganese nitrate in 30 mL of deionized water;
step three, mixing the solution obtained in the step two with the solution obtained in the step one, and stirring for more than 12 hours;
fourthly, adding 10 mL of urotropine aqueous solution with the molar concentration of 1M into the solution obtained in the third step, and reacting for 6 hours at the constant temperature of 80 ℃;
fifthly, cleaning and drying the product obtained in the fourth step, and etching for more than 3 times by adopting a sodium hydroxide solution with the molar concentration of 4M;
and sixthly, cleaning and drying the product obtained in the fifth step to obtain the hollow mesoporous carbon sphere @ nickel cobalt manganese hydroxide nano composite material.
With reference to fig. 1, the particle size of the synthesized hollow mesoporous carbon sphere is about 360 nm, and the growth conditions of the nickel-cobalt-manganese hydroxide nanosheets inside and outside the hollow mesoporous carbon sphere can be regulated and controlled by changing the content of the hollow mesoporous carbon sphere.
With reference to fig. 2, nanoflowers assembled by nickel-cobalt-manganese hydroxide nanosheets with a size of about 340 nm are encapsulated inside the hollow mesoporous carbon sphere, and the nickel-cobalt-manganese hydroxide nanosheets with a size of about 13 nm are uniformly wrapped on the outer surface of the hollow mesoporous carbon sphere.
With reference to fig. 3, an XRD chart shows that the nickel cobalt manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite is successfully prepared.
With reference to fig. 4, it is shown that the prepared nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite has a relatively high surface area and a rich pore structure.
With reference to fig. 5, it is shown that the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite has higher specific mass capacity and rate capability than pure nickel-cobalt-manganese hydroxide.
With reference to fig. 6, the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite has a higher volume-specific capacitance than the hollow mesoporous carbon sphere @ nickel-cobalt-manganese hydroxide nanocomposite.
With reference to fig. 7, the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite material is 10A g-1The capacity retention rate of 5000 cycles of circulation under the current density is maintained at 86.8%, and the circulation stability is excellent.
From the above experimental results, the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite obtained in example 2 has the best structure and the best electrochemical performance.
Claims (8)
1. The nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nano composite material is characterized in that nickel-cobalt-manganese hydroxide nanosheets grow in a limited area on the inner surface and the outer surface of a hollow mesoporous carbon sphere in the composite material.
2. The method for preparing the nickel-cobalt-manganese hydroxide @ hollow mesoporous carbon sphere nanocomposite material according to claim 1, comprising the following steps of:
firstly, putting a nitrate mixed solution of nickel, cobalt and manganese into a hollow mesoporous carbon sphere precursor solution, and stirring for a period of time;
and step two, adding a urotropine solution into the solution obtained in the step one, reacting for a period of time at a constant temperature, cleaning the obtained product, and drying to obtain the composite material.
3. The method of claim 2, wherein the hollow mesoporous carbon sphere precursor solution is prepared by:
(1) adding tetraethyl orthosilicate into a mixed solution containing absolute ethyl alcohol, deionized water and ammonia water, stirring in a constant-temperature water bath at the temperature of 20-30 ℃ for a period of time, adding resorcinol, continuing stirring, adding a formaldehyde solution, and stirring for more than 24 hours;
(2) cleaning the precipitate obtained in the step (1), drying, and carrying out treatment at 2 ℃ for min in a nitrogen atmosphere-1The temperature rising rate is increased to 700 +/-10 ℃ and the reaction is carried out for 5 hours at constant temperature;
(3) and (3) etching the product obtained in the step (2) by adopting a hydrofluoric acid solution, cleaning, drying, and ultrasonically dispersing uniformly in deionized water to obtain a hollow mesoporous carbon sphere precursor solution.
4. The method of claim 2, wherein the molar ratio of nickel, cobalt and manganese is 1: 1: 1.
5. the method according to claim 2, wherein the mass ratio of the hollow mesoporous carbon spheres to the nickel nitrate in the nitrate mixed solution of nickel, cobalt and manganese is 0.03 to 0.17.
6. The method of claim 2, wherein the molar ratio of urotropin to metal ions in the mixed solution of nickel, cobalt and manganese nitrates is 1.67: 1.
7. the method according to claim 2, wherein the stirring time in the first step is 12 hours or more.
8. The method of claim 2, wherein in the second step, the reaction is carried out at 80 ± 5 ℃ for 5-7 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105914345A (en) * | 2016-05-10 | 2016-08-31 | 湖南大学 | Hollow nano transition metal sulfide/carbon composite material and preparation method |
| CN110828190A (en) * | 2018-08-10 | 2020-02-21 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
| CN111446086A (en) * | 2020-03-09 | 2020-07-24 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanosheet/foamed nickel @ nitrogen-doped carbon electrode material |
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| CN105914345A (en) * | 2016-05-10 | 2016-08-31 | 湖南大学 | Hollow nano transition metal sulfide/carbon composite material and preparation method |
| CN110828190A (en) * | 2018-08-10 | 2020-02-21 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
| CN111446086A (en) * | 2020-03-09 | 2020-07-24 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanosheet/foamed nickel @ nitrogen-doped carbon electrode material |
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|---|---|---|---|---|
| CN115057488A (en) * | 2022-07-12 | 2022-09-16 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode material with special morphology and preparation method and application thereof |
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