CN113428850A - Method for preparing three-shell-layer phosphate hydroxide hollow nano cage material by layer-by-layer assembly method at room temperature - Google Patents
Method for preparing three-shell-layer phosphate hydroxide hollow nano cage material by layer-by-layer assembly method at room temperature Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000002091 nanocage Substances 0.000 title claims abstract description 28
- TWHXWYVOWJCXSI-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O TWHXWYVOWJCXSI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000707 layer-by-layer assembly Methods 0.000 title claims abstract description 20
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 27
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 27
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910020630 Co Ni Inorganic materials 0.000 claims description 6
- 229910002440 Co–Ni Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 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 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011796 hollow space material Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 29
- 239000002086 nanomaterial Substances 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- -1 transition metal hydroxide phosphate Chemical class 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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- 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
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Abstract
The invention provides a layer-by-layer assembly method for preparing a three-shell-layer phosphate hydroxide hollow nano cage material at a room temperature, and the method is applied to the field of supercapacitors. Firstly, preparing a regular dodecahedron precursor with uniform size by a room-temperature standing method under the room-temperature condition, and finally preparing the dianion (hydroxyl and phosphate radical) doped three-shell-layer phosphate hydroxide hollow nano cage through layer-by-layer coating and etching circulation. The chemical molecular formula of the nano cage can be named as CoxNi1‑x(PO4)y(OH)2‑3yBy changing the amount of nickel salt and the reaction time during the synthesis process, the variation of x within the range of 0.15-0.4 can be realized, and by changing the amount of sodium phosphate and the reaction time, the variation of y within the range of 0.2-0.4 can be realized. Due to the unique multi-shell structure, the amorphous structure and the synergistic effect of mutual doping of anions and cations, the product has excellent application performance of the super capacitor. The method provides a preparation method of a component-adjustable tri-shell hydroxide phosphate hollow nano cage material, provides an effective synthetic route for the preparation of multi-shell anion co-doped hollow materials, and plays an important reference role in the expansion and application of the materials in the field of supercapacitors.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a layer-by-layer assembly preparation method of a phosphate hydroxide hollow nano cage material with a multi-shell structure and application of a super capacitor of the phosphate hydroxide hollow nano cage material.
Background
Hollow nano materials attract the extensive attention of researchers at home and abroad due to the huge application potential in the aspects of drug transmission, multifunctional catalysis, fluorescence sensing and energy storage. At present, in the field of electrochemical energy storage, researchers design and synthesize a large number of hollow nano materials with different shapes and compositions in order to obtain higher electrochemical energy storage performance. Most of reported hollow nano materials are in a single-shell structure, and although higher specific mass capacity is provided, the specific volume capacity is relatively smaller due to lower tap density, so that the applicability of the hollow nano materials is limited. The hollow nano material with the multi-shell structure can keep the original structural advantages of the hollow material, and the unique nested structure can also obviously increase the tap density of the material, so that the aims of high-quality specific capacity and high-volume specific capacity are fulfilled. However, the multi-shell materials reported at present are still limited, mainly due to the complex interfacial process of the multi-shell interface, surface force and ostwald ripening effect during the preparation of the materials, resulting in the destruction of the multi-layer structure. Therefore, how to prepare the multi-shell hollow nano-material in a gentle and controllable way remains a significant challenge in the field.
The transition metal phosphate material has a unique open framework structure, can provide more electrolyte diffusion channels and active centers, and is an ideal electrode material of the super capacitor. In order to obtain excellent performance of the super capacitor, researchers prepare nano phosphate materials with different morphologies, such as: nanoflower, nanosheets, nanospheres, nanorods, and the like. However, transition metal phosphate nanomaterials with hollow structures have been reported, mainly because the coordination of phosphate ions has strong directionality, and they are easily preferentially aggregated along a direction with low energy, which is not favorable for the formation of hollow structures. In addition, the anion doping of the transition metal phosphate can remarkably improve the conductivity and porosity of the phosphate nano material, thereby enhancing the specific capacity and the cycling stability of the material.
At present, a multi-shell nano material based on transition metal hydroxide phosphate is not reported. The method for preparing the high-performance multi-shell-layer phosphate hydroxide hollow electrode material by a mild and controllable method has important significance.
Disclosure of Invention
The invention provides a layer-by-layer assembly strategy, a double-anion (hydroxyl and phosphate radical) doped hollow nanometer cage material with a three-shell structure is prepared at room temperature, and the material shows ultrahigh specific capacity and excellent cycling stability when applied to a super capacitor.
In order to realize the preparation of multi-shell materials and the doping of double anions (hydroxide radical and phosphate radical), the invention can be realized by the following technical routes:
(1) preparation of self-sacrifice template: respectively dissolving cobalt nitrate hexahydrate (1 part by mass) and dimethyl imidazole (2-MIN, 0.5-2 parts by mass) in methanol, mixing the two solutions, and standing at room temperature for 16-32 hours to obtain a self-sacrifice template, which is named as ZIF-67.
(2) Preparing a three-shell-layer hydroxide phosphate hollow nano cage material by a layer-by-layer assembly method: firstly, assembling a first layer, namely, dispersing ZIF-67(1 part by mass) in a solution (200 parts by mass) containing metal nickel salt (1.2-3 parts by mass), and stirring for 30 minutes at room temperature to obtain a solution of cobalt nickel hydroxide coated ZIF-67 core-shell (named as LDH @ ZIF-67); and adding an aqueous solution (200-1000 parts by mass) containing sodium phosphate (0.5-1.5 parts by mass) into the solution, stirring at room temperature for 30-90 minutes, centrifuging and washing for multiple times to obtain a core-shell structure (named as O-LDH @ ZIF-67) with a ZIF-67 core separated from a Co-Ni LDH shell layer. Secondly, assembling a second layer, namely dispersing O-LDH @ ZIF-67(1 part by mass) in a solution (500 plus 2000 parts by mass) containing metal nickel salt (1.6-6.4 parts by mass), and stirring for 30 minutes at room temperature to obtain a solution of a ZIF-67 core-shell structure (named as DS-LDH @ ZIF-67) coated by two layers of nickel hydroxide shells on a new cobalt nickel hydroxide coated ZIF-67 core; and adding an aqueous solution (500-2000 parts by mass) containing sodium phosphate (0.8-3.2 parts by mass) into the solution, stirring at room temperature for 10-30 minutes, centrifuging and washing for multiple times to obtain a double-shell single-core structure (named as O-DS-LDH @ ZIF-67) with a ZIF-67 core separated from an internal Co-Ni LDH shell layer. Thirdly, assembling the third layer, namely dispersing O-LDH @ ZIF-67(1 part by mass) in a solution (500 plus 2000 parts by mass) containing metal nickel salt (1.6-6.4 parts by mass), and stirring at room temperature for 10-30 minutes to obtain a solution of a ZIF-67 core-shell structure (named TS-LDH @ ZIF-67) coated by three layers of cobalt nickel hydroxide shells on a ZIF-67 core coated by cobalt nickel hydroxide; adding an aqueous solution (500-2000 parts by mass) containing sodium phosphate (0.8-3.2 parts by mass) into the solution, stirring at room temperature for 2-12 hours, centrifuging and washing for multiple times to obtain the phosphate hydroxide hollow nanocage material with a three-shell structure.
As a further feature of the present invention: the standing time of the step (1) is 16-32 hours, the obtained self-sacrifice precursors all present a typical regular dodecahedron nano cage-shaped structure, and the nano size is between 600-900 nm; the difference of the sizes of the precursors can be only influenced by different standing time in the process, the subsequent layer-by-layer assembly process is also applicable, the final three-shell-layer hydroxide phosphate nano cage structure can be formed, and only the performance can be different.
As a further feature of the present invention: in the solution of the metal nickel salt in the step (2), the types of the metal nickel salt (nickel chloride, nickel nitrate and nickel sulfate) and the types of the solvent (methanol, ethanol, acetone and 1, 4-dioxane) have little influence on the final appearance of the product, and only the 1, 4-dioxane is used as the solvent, so that the performance of the product is reduced.
As a further aspect of the inventionIs characterized in that: the dosage of the metallic nickel salt in the step (2) can influence the product CoxNi1-x(PO4)y(OH)2-3yAnd x in (b) varies from 0.15 to 0.4. When the amount of metal nickel salt used in the assembling process of any one layer in the first layer assembly, the second layer assembly and the third layer assembly is reduced, the value of x is increased; on the contrary, when the amount of nickel salt used in any layer of assembly process is increased, the value of x is reduced.
As a further feature of the present invention: the dosage of the sodium phosphate in the step (2) and the reaction time of the product in the sodium phosphate solution influence the product CoxNi1-x(PO4)y(OH)2-3yAnd y in (b) varies within the range of 0.2 to 0.4. When the sodium phosphate used in the assembly process of any one layer is reduced and the reaction time is reduced in the assembly of the first layer, the assembly of the second layer and the assembly of the third layer, the y value is reduced; on the contrary, when the amount of sodium phosphate used in the assembly of any layer is increased and the reaction time is increased, the value of y is increased.
As a further feature of the present invention: the amount of the sodium phosphate in the step (2) and the reaction time of the product in the sodium phosphate solution influence the sizes of the intermediate shell and the innermost shell in the product. In the first layer assembling process, the size of the intermediate shell layer and the size of the innermost shell layer are influenced by the using amount of sodium phosphate and the reaction time of a product in a sodium phosphate solution, the larger the using amount of the sodium phosphate and the longer the reaction time are, the smaller the size of the intermediate shell layer and the size of the innermost shell layer are, and otherwise, the smaller the using amount and the shorter the reaction time are, the larger the size of the intermediate shell layer and the size of the innermost shell layer are. And secondly, in the second layer assembling process, the size of the innermost shell layer is only influenced by the using amount of sodium phosphate and the reaction time of the product in the sodium phosphate solution, and the influence process is consistent with the first layer assembling process.
As a further feature of the present invention: the size of the prepared hollow three-shell nano cage structure is 600-900nm, and the thickness of each shell is 30-80 nm.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
as the inventionFurther features of (a): when the three-shell-layer phosphate hydroxide hollow nano cage prepared by the method is used for the electrode material of the super capacitor, the volume of the three-shell-layer phosphate hydroxide hollow nano cage is 2mAcm-2The specific capacity is up to 3012mF cm-2And the specific capacity of the cycle 6000 can be kept at 93.06 percent.
Detailed Description
The technical features of the present invention will be described below with reference to specific experimental schemes and drawings, but the present invention is not limited thereto. The test methods described in the following examples are all conventional methods unless otherwise specified; the apparatus and materials are commercially available, unless otherwise specified.
Example 1
A method for preparing a three-shell-layer phosphate hydroxide hollow nanocage material at room temperature by a layer-by-layer assembly method is shown in a schematic diagram in figure 1, and comprises the following steps:
(1) preparation of self-sacrifice template: cobalt nitrate hexahydrate (1 part by mass) and dimethylimidazole (2-MIN, 0.5-2 parts by mass) were dissolved in water, respectively, and then the above two solutions were mixed and left to stand at room temperature for 16-32 hours to obtain a self-immolative template (see fig. 2), and was named ZIF-67.
(2) Preparing a three-shell-layer hydroxide phosphate hollow nano cage material by a layer-by-layer assembly method: firstly, assembling a first layer, namely, dispersing ZIF-67(1 part by mass) in an ethanol solution (500 parts by mass) containing nickel nitrate (1.6 parts by mass), and stirring at room temperature for 0.5 hour to obtain an ethanol solution of cobalt nickel hydroxide coated ZIF-67 core shell (named as LDH @ ZIF-67, shown in figure 3); to the above solution was added an aqueous solution (500 parts by mass) containing sodium phosphate (0.8 part by mass), stirred at room temperature for 1 hour, centrifuged and washed several times to obtain a core-shell structure (named O-LDH @ ZIF-67) in which the ZIF-67 core was detached from the Co-Ni LDH shell layer (see fig. 4). Secondly, assembling a second layer, namely dispersing O-LDH @ ZIF-67(1 part by mass) in an ethanol solution (1000 parts by mass) containing nickel nitrate (3.2 parts by mass), and stirring at room temperature for 0.5 hour to obtain an ethanol solution of a ZIF-67 core-shell structure (named DS-LDH @ ZIF-67, as shown in figure 5) coated by two nickel hydroxide shells on a cobalt nickel hydroxide coated ZIF-67 core; to the above solution was added an aqueous solution (1000 parts by mass) containing sodium phosphate (1.6 parts by mass), stirred at room temperature for 10 minutes, centrifuged and washed several times to obtain a double-shell single-core structure (named O-DS-LDH @ ZIF-67, as shown in fig. 6) in which the ZIF-67 core was detached from the inner Co-Ni LDH shell layer. Thirdly, assembling a third layer, namely dispersing O-LDH @ ZIF-67(1 part by mass) in an ethanol solution (1000 parts by mass) containing nickel nitrate (3.2 parts by mass), and stirring for 15 minutes at room temperature to obtain an ethanol solution of a ZIF-67 core-shell structure (named TS-LDH @ ZIF-67, as shown in figure 7) coated by three layers of cobalt-nickel hydroxide shells on a new cobalt-nickel hydroxide coated ZIF-67 core; to the above solution was added an aqueous solution (1000 parts by mass) containing sodium phosphate (1.6 parts by mass), stirred at room temperature for 15 minutes, centrifuged and washed several times to obtain a phosphate hydroxide hollow nanocage material (designated TS-CNHP, fig. 8) having a tri-shell structure.
XRD spectrum test shows that TS-LDH @ ZIF-67 is in an amorphous structure (as shown in figure 9); the XPS spectrum shows that Co, Ni, P and O elements coexist TS-LDH @ ZIF-67, and the ratio of Co to Ni to P is 2:6:3 (as shown in figure 10); the thermogravimetric test showed a significant weight loss between 200-380 degrees, indicating the presence of a large amount of hydroxide anions inside the material (see fig. 11). The molecular formula of the product obtained by combining the analysis is Co0.25Ni0.75(PO4)3(OH)7·8H2And O. The electrochemical test result shows that the material shows obvious pseudocapacitance behavior (as shown in figure 12) at 2mA cm-2The specific capacity is up to 3012mF cm-2The specific capacity of the 6000 circulation round can be kept at 93.06% (as shown in figure 13).
Example 2
A method for preparing a three-shell-layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) the self-immolative template was prepared as in example 1.
(2) The layer-by-layer assembly method was similar to example 1 except that the first layer was assembled with the amount of metallic nickel salt adjusted to 1.2 parts by mass, the second layer was assembled with the amount of metallic nickel salt adjusted to 1.6 parts by mass, and the third layer was assembled with the amount of metallic nickel salt adjusted to 1.6 parts by mass.
The proportion of Co and Ni of the obtained product is obviously changed, and the molecular formula of the product is Co0.4Ni0.6(PO4)0.4(OH)0.8·8H2O。
Example 3
A method for preparing a three-shell-layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) the self-immolative template was prepared as in example 1.
(2) The layer-by-layer assembly method was similar to example 1 except that the first layer was assembled with the amount of metallic nickel salt adjusted to 3 parts by mass, the second layer was assembled with the amount of metallic nickel salt adjusted to 6.4 parts by mass, and the third layer was assembled with the amount of metallic nickel salt adjusted to 6.4 parts by mass.
The proportion of Co and Ni of the obtained product is obviously changed, and the molecular formula of the product is Co0.15Ni0.85(PO4)0.4(OH)0.8·8H2O。
Example 4
A method for preparing a three-shell-layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) the self-immolative template was prepared as in example 1.
(2) The preparation process of the layer-by-layer assembly method is similar to that of example 1, except that the first layer is assembled, the amount of sodium phosphate is adjusted to 0.5 part by mass, and the mixture is stirred for 30 minutes at room temperature; assembling the second layer, adjusting the amount of the sodium phosphate to 0.8 part by mass, and stirring for 10 minutes at room temperature; thirdly, assembling the third layer, adjusting the amount of the sodium phosphate to 0.8 part by mass, stirring for 2 hours at room temperature
To obtain PO in the product4 3-And OH-The proportion of anions is obviously changed, and the molecular formula of the product is Co0.25Ni0.75(PO4)0.2(OH)1.4·8H2O。
Example 5
A method for preparing a three-shell-layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) the self-immolative template was prepared as in example 1.
(2) The preparation process of the layer-by-layer assembly method is similar to that of example 1, except that the first layer is assembled, the amount of sodium phosphate is adjusted to 1.5 parts by mass, and the mixture is stirred for 90 minutes at room temperature; secondly, assembling the second layer, adjusting the amount of the sodium phosphate to 3.2 parts by mass, and stirring for 30 minutes at room temperature; thirdly, assembling the third layer, adjusting the amount of the sodium phosphate to 3.2 parts by mass, stirring for 12 hours at room temperature
To obtain PO in the product4 3-And OH-The proportion of anions is obviously changed, and the molecular formula of the product is Co0.25Ni0.75(PO4)0.5(OH)0.5·8H2O。
The description of the disclosed embodiments is not intended to limit the scope of the invention, but is instead provided to describe the invention. Accordingly, the scope of the present invention is not limited by the above embodiments, but is defined by the claims or their equivalents.
Description of the drawings:
FIG. 1: example 1 a schematic diagram of a three-shell layer phosphate hydroxide hollow nanocage material prepared by a layer-by-layer assembly method;
FIG. 2: SEM of ZIF-67 obtained in example 1;
FIG. 3: scanning electron micrographs of LDH @ ZIF-67 obtained in example 1;
FIG. 4: transmission electron micrograph of O-LDH @ ZIF-67 obtained in example 1;
FIG. 5: a transmission electron micrograph of DS-LDH @ ZIF-67 obtained in example 1;
FIG. 6: a transmission electron micrograph of O-DS-LDH @ ZIF-67 obtained in example 1;
FIG. 7: a transmission electron micrograph of TS-LDH @ ZIF-67 obtained in example 1;
FIG. 8: transmission electron microscopy of the TS-CNHP obtained in example 1;
FIG. 9: an X-ray spectrum of the TS-CNHP obtained in example 1;
FIG. 10: XPS plots of TS-CNHP obtained in example 1;
FIG. 11: TGA Profile of TS-CNHP obtained in example 1
FIG. 12: cyclic voltammogram (a) and constant-current charge-discharge diagram (b) of the TS-CNHP obtained in example 1;
FIG. 13: specific capacity cycling profile of the TS-CNHP obtained in example 1.
Claims (5)
1. A method for preparing a three-shell-layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method at room temperature is characterized by comprising the following steps:
(1) preparation of self-sacrifice template: respectively dissolving cobalt nitrate hexahydrate (1 part by mass) and dimethyl imidazole (2-MIN, 0.5-2 parts by mass) in methanol, mixing the two solutions, and standing at room temperature for 16-32 hours to obtain the ZIF-67 self-sacrifice template.
(2) Preparing a three-shell-layer hydroxide phosphate hollow nano cage material by a layer-by-layer assembly method: firstly, assembling a first layer, namely, dispersing ZIF-67(1 part by mass) in a solution (200 parts by mass) containing metal nickel salt (1.2-3 parts by mass), and stirring for 30 minutes at room temperature to obtain a solution of cobalt nickel hydroxide coated ZIF-67 core-shell (named as LDH @ ZIF-67); and adding an aqueous solution (200-1000 parts by mass) containing sodium phosphate (0.5-1.5 parts by mass) into the solution, stirring at room temperature for 30-90 minutes, centrifuging and washing for multiple times to obtain a core-shell structure (named as O-LDH @ ZIF-67) with a ZIF-67 core separated from a Co-Ni LDH shell layer. Secondly, assembling a second layer, namely dispersing O-LDH @ ZIF-67(1 part by mass) in a solution (500 plus 2000 parts by mass) containing metal nickel salt (1.6-6.4 parts by mass), and stirring for 30 minutes at room temperature to obtain a solution of a ZIF-67 core-shell structure (named as DS-LDH @ ZIF-67) coated by two layers of nickel hydroxide shells on a new cobalt nickel hydroxide coated ZIF-67 core; and adding an aqueous solution (500-2000 parts by mass) containing sodium phosphate (0.8-3.2 parts by mass) into the solution, stirring at room temperature for 10-30 minutes, centrifuging and washing for multiple times to obtain a double-shell single-core structure (named as O-DS-LDH @ ZIF-67) with a ZIF-67 core separated from an internal Co-Ni LDH shell layer. Thirdly, assembling the third layer, namely dispersing O-LDH @ ZIF-67(1 part by mass) in a solution (500 plus 2000 parts by mass) containing metal nickel salt (1.6-6.4 parts by mass), and stirring at room temperature for 10-30 minutes to obtain a solution of a ZIF-67 core-shell structure (named TS-LDH @ ZIF-67) coated by three layers of cobalt nickel hydroxide shells on a ZIF-67 core coated by cobalt nickel hydroxide; adding an aqueous solution (500-2000 parts by mass) containing sodium phosphate (0.8-3.2 parts by mass) into the solution, stirring at room temperature for 2-12 hours, centrifuging and washing for multiple times to obtain the phosphate hydroxide hollow nanocage material with a three-shell structure.
2. The method of claim 1, wherein: the metal nickel salt used in the step (2) is one or a mixture of more than one of nickel chloride, nickel nitrate and nickel sulfate, and the solvent of the metal nickel salt is any one of methanol, ethanol, acetone and 1, 4-dioxane.
3. The method of claim 1, wherein: prepared cobalt-nickel base hydroxide phosphate CoxNi1-x(PO4)y(OH)2-3yWherein x ranges from 0.15 to 0.4 and y ranges from 0.2 to 0.5.
4. The method of claim 1, wherein: the prepared product is a hollow three-shell nano cage structure, the size is 600-900nm, and the thickness of each shell is 30-80 nm.
5. The application of the three-shell-layer phosphate hydroxide hollow nanocage material prepared by the preparation method of claim 1, which is characterized in that: the application refers to the application of the three-shell-layer phosphate hydroxide hollow nano cage material in the super capacitor.
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