CN113428850B - Method for preparing three-shell layer hydrogen phosphate hollow nano cage material by layer-by-layer assembly method at room temperature - Google Patents
Method for preparing three-shell layer hydrogen phosphate hollow nano cage material by layer-by-layer assembly method at room temperature Download PDFInfo
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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 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 room temperature condition, and finally preparing the dianion (hydroxyl and phosphate) doped three-shell-layer phosphate hydroxide hollow nano cage by layer-by-layer cladding and etching circulation. The chemical molecular formula of the nanocage can be named as Co x Ni 1‑x (PO 4 ) y (OH) 2‑3y The change of x in the range of 0.15-0.4 can be realized by changing the dosage and the reaction time of nickel salt in the synthesis process, and the change of y in the range of 0.2-0.4 can be realized by changing the dosage and the reaction time of sodium phosphate. The product has excellent supercapacitor application performance due to the unique multi-shell structure, the amorphous structure and the synergistic effect of the mutual doping of anions and cations. The method provides a preparation method of the three-shell-layer phosphate hydroxide hollow nano cage material with adjustable components, provides an effective synthetic route for the preparation of the multi-shell-layer anion co-doped hollow material, and plays an important reference role in expanding the application of the material in the field of super capacitors.
Description
Technical Field
The invention belongs to the technical field of nano materials, and in particular relates to a layer-by-layer assembly preparation method of a phosphate hydroxide hollow nano cage material with a multi-shell structure and an application of a super capacitor of the material.
Background
The hollow nano material attracts wide attention of researchers at home and abroad because of the great application potential of the hollow nano material in aspects of drug transmission, multifunctional catalysis, fluorescence sensing and energy storage. Currently, in the field of electrochemical energy storage, in order to obtain higher electrochemical energy storage performance, researchers design and synthesize a large number of hollow nano materials with different shapes and compositions. Most reported hollow nano materials are of a single shell structure, and although the hollow nano materials provide higher mass specific capacity, the hollow nano materials have lower tap density and relatively smaller volume specific capacity, so that the applicability of the hollow nano materials is limited. The hollow nano material with the multi-shell structure not only can keep the original structural advantages of the hollow material, but also can obviously increase the tap density of the material due to the unique nested structure, thereby simultaneously meeting the purposes of high mass specific capacity and high volume specific capacity. However, the multi-shell materials reported so far remain limited, mainly due to the complex interfacial processes, surface forces and ostwald ripening effects of the multi-shell interfaces during the preparation of the materials, resulting in the destruction of the multi-layer structure. Thus, how to gently and controllably prepare multi-shell hollow nanomaterials remains an important challenge in the art.
The transition metal phosphate material has a unique open framework structure, can provide more electrolyte diffusion channels and active centers, and is an ideal supercapacitor electrode material. In order to obtain excellent supercapacitor performance, researchers have prepared nano phosphate materials of different morphologies, such as: nanoflower, nanoplatelets, nanospheres, nanorods, and the like. However, transition metal phosphate nano materials with hollow structures are rarely reported, mainly because the coordination of phosphate ions has strong directionality, and is easy to gather preferentially along a direction with lower energy, so that the formation of the hollow structures is not favored. In addition, the anion doping of the transition metal phosphate can significantly improve the conductivity and porosity of the phosphate nanomaterial, thereby enhancing the specific capacity and cycling stability of the material.
At present, multi-shell nano materials based on transition metal hydrogen phosphate are not reported yet. The preparation of 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 strategy of layer-by-layer assembly, and a hollow nano cage material with a three-shell structure doped with dianion (hydroxyl and phosphate) is prepared at room temperature, and the material shows ultrahigh specific capacity and excellent cycle stability when being applied to super capacitors.
In order to realize the preparation of multi-shell materials and the doping of dianions (hydroxyl and phosphate), the invention can be realized by the following technical routes:
(1) Preparation of self-sacrifice templates: cobalt nitrate hexahydrate (1 part by mass) and dimethyl imidazole (2-MIN, 0.5-2 parts by mass) were dissolved in methanol, respectively, and then the above two solutions were mixed and allowed to stand at room temperature for 16-32 hours, to obtain a self-sacrifice template, and designated as ZIF-67.
(2) Preparing a three-shell layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method: (1) the first layer is assembled, ZIF-67 (1 part by mass) is dispersed in a solution (200-1000 parts by mass) containing metallic nickel salt (1.2-3 parts by mass), and the mixture is stirred at room temperature for 30 minutes to obtain a solution of cobalt nickel hydroxide coated ZIF-67 core-shell (named as LDH@ZIF-67); to the above solution, an aqueous solution (200-1000 parts by mass) containing sodium phosphate (0.5-1.5 parts by mass) was added, stirred at room temperature for 30-90 minutes, centrifuged and washed multiple times to obtain a core-shell structure (designated as O-ldh@zif-67) in which the ZIF-67 core and Co-Ni LDH shell layer are separated. (2) The second layer of assembly, wherein O-LDH@ZIF-67 (1 part by mass) is dispersed in a solution (500-2000 parts by mass) containing metallic nickel salt (1.6-6.4 parts by mass), and stirring is carried out for 30 minutes at room temperature, so as to obtain a solution of a new cobalt nickel hydroxide coated ZIF-67 core-shell structure (named DS-LDH@ZIF-67) coated by two layers of nickel hydroxide shells on a ZIF-67 core; to the above solution, an aqueous solution (500-2000 parts by mass) containing sodium phosphate (0.8-3.2 parts by mass) was added, stirred at room temperature for 10-30 minutes, centrifuged and washed multiple times to obtain a double-shell single-core structure (designated as O-DS-ldh@zif-67) in which the ZIF-67 core is separated from the inner Co-Ni LDH shell layer. (3) The third layer is assembled, O-LDH@ZIF-67 (1 part by mass) is dispersed in a solution (500-2000 parts by mass) containing metallic nickel salt (1.6-6.4 parts by mass), and stirring is carried out for 10-30 minutes at room temperature, so that a solution of a three-layer cobalt nickel hydroxide coated ZIF-67 core-shell structure (named TS-LDH@ZIF-67) on a cobalt nickel hydroxide coated ZIF-67 core is obtained; adding aqueous solution (500-2000 parts by mass) containing sodium phosphate (0.8-3.2 parts by mass) into the solution, stirring for 2-12 hours at room temperature, centrifuging and washing for multiple times to obtain the phosphate hydroxide hollow nano cage 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, and the obtained self-sacrifice precursor presents a typical regular dodecahedron nano cage structure, and the nano size is 600-900 nm; in the process, different standing time only affects the difference of the sizes of the precursors, the subsequent layer-by-layer assembly process is also applicable, and the final three-shell layer hydrogen phosphate nano cage structure can be formed, but the performances are 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 as the solvent can cause the performance of the product to be reduced.
As a further feature of the present invention: the amount of the metal nickel salt in the step (2) can influence the Co product x Ni 1-x (PO 4 ) y (OH) 2-3y X in (a) varies from 0.15 to 0.4. When the metal nickel salt used in any one layer assembly process is reduced in the (1) first layer assembly, (2) second layer assembly and (3) third layer assembly, the x value is increased; on the contrary, when the nickel salt used in any one layer of the assembly process is increased, the x value becomes smaller.
As a further feature of the present invention: the amount of sodium phosphate used in step (2) and the reaction time of the product in the sodium phosphate solution affect the product Co x Ni 1-x (PO 4 ) y (OH) 2-3y In which y is in the range of 0.2 to 0.4And (3) a change. When the sodium phosphate used in any one layer assembly process is reduced and the reaction time is reduced in (1) first layer assembly, (2) second layer assembly and (3) third layer assembly, the y value is reduced; on the contrary, when the amount of sodium phosphate used in any one layer assembly process is increased and the reaction time is increased, the y value is increased.
As a further feature of the present invention: the amount of sodium phosphate used in step (2) and the reaction time of the product in the sodium phosphate solution will affect the size of the intermediate and innermost shell layers in the product. (1) In the first layer assembly process, the size of the middle shell layer and the innermost shell layer can be influenced by the amount of sodium phosphate and the reaction time of the product in the sodium phosphate solution, the larger the amount of sodium phosphate and the longer the reaction time are, the smaller the size of the middle shell layer and the innermost shell layer can be caused, and otherwise, the smaller the amount and the short time are, the larger the size of the middle shell layer and the innermost shell layer can be caused. (2) In the second layer assembly process, the dosage of sodium phosphate and the reaction time of the product in the sodium phosphate solution only affect the size of the innermost shell layer, and the affecting process is consistent with the first layer assembly process (1).
As a further feature of the present invention: the prepared hollow three-shell nano cage structure has the size of 600-900nm and the thickness of each shell layer of 30-80nm.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
as a further feature of the present invention: when the three-shell-layer phosphate hydroxide hollow nano cage prepared by the invention is used for super capacitor electrode materials, the three-shell-layer phosphate hydroxide hollow nano cage is 2mAcm in length -2 At a current density of up to 3012mF cm -2 The specific capacity of 6000 cycles can be kept at 93.06%.
Detailed Description
The technical features of the present invention will be described with reference to the following specific experimental schemes and drawings, but the present invention is not limited thereto. The test methods described in the examples below, unless otherwise specified, are all conventional; the apparatus and materials are commercially available unless otherwise specified.
Example 1
A method for preparing a three-shell layer hydrogen phosphate hollow nano cage material by a layer-by-layer assembly method at room temperature is shown in a schematic diagram as shown in figure 1, and comprises the following steps:
(1) Preparation of self-sacrifice templates: cobalt nitrate hexahydrate (1 part by mass) and dimethyl imidazole (2-MIN, 0.5-2 parts by mass) were dissolved in water, respectively, and then the above two solutions were mixed and allowed to stand at room temperature for 16-32 hours to obtain a self-sacrifice template (see fig. 2), and designated as ZIF-67.
(2) Preparing a three-shell layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method: (1) the first layer was assembled, ZIF-67 (1 part by mass) was dispersed in an ethanol solution (500 parts by mass) containing nickel nitrate (1.6 parts by mass), and stirred at room temperature for 0.5 hours to obtain an ethanol solution of cobalt nickel hydroxide-coated ZIF-67 core-shell (named LDH@ZIF-67, as shown in FIG. 3); to the above solution was added an aqueous solution (500 parts by mass) containing sodium phosphate (0.8 parts by mass), stirred at room temperature for 1 hour, centrifuged and washed several times to obtain a core-shell structure in which the ZIF-67 core and Co-Ni LDH shell were separated (designated as O-LDH@ZIF-67, as shown in FIG. 4). (2) A second layer of assembly, wherein O-LDH@ZIF-67 (1 part by mass) is dispersed in an ethanol solution (1000 parts by mass) containing nickel nitrate (3.2 parts by mass), and stirring is carried out for 0.5 hours at room temperature, so as to obtain an ethanol solution of a two-layer nickel hydroxide shell-coated ZIF-67 core-shell structure (named DS-LDH@ZIF-67 as shown in figure 5) 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 (designated as O-DS-ldh@zif-67, as shown in fig. 6) in which the ZIF-67 core was separated from the inner Co-Ni LDH shell layer. (3) The third layer is assembled, O-LDH@ZIF-67 (1 part by mass) is dispersed in ethanol solution (1000 parts by mass) containing nickel nitrate (3.2 parts by mass), and stirring is carried out for 15 minutes at room temperature, so that ethanol solution of a three-layer cobalt nickel hydroxide coated ZIF-67 core-shell structure (named TS-LDH@ZIF-67 as shown in figure 7) on a new cobalt nickel hydroxide coated ZIF-67 core is obtained; 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 having a three-shell structure (designated as TS-CNHP, as shown in fig. 8).
XRD spectrumTests show that TS-LDH@ZIF-67 is of an amorphous structure (as shown in figure 9); XPS spectrum shows that Co, ni, P and O elements coexist in TS-LDH@ZIF-67, and the ratio of Co to Ni to P is 2:6:3 (as shown in figure 10); thermogravimetric testing showed significant weight loss between 200 and 380 degrees, indicating the presence of significant amounts of hydroxide anions within the material (see fig. 11). The molecular formula of the product obtained by combining the analysis is Co 0.25 Ni 0.75 (PO 4 ) 3 (OH) 7 ·8H 2 O. The electrochemical test result shows that the material shows obvious pseudocapacitance behavior (shown in figure 12) at 2mA cm -2 At a current density of up to 3012mF cm -2 The cycle 6000 round capacity can be kept 93.06% (as in fig. 13).
Example 2
A method for preparing a three-shell layer hydrogen phosphate hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) The preparation of the self-sacrifice template was the same as in example 1.
(2) The layer-by-layer assembly method was similar to example 1, except that (1) the first layer was assembled, the amount of the metal nickel salt was adjusted to 1.2 parts by mass, (2) the second layer was assembled, the amount of the metal nickel salt was adjusted to 1.6 parts by mass, and (3) the third layer was assembled, the amount of the metal nickel salt was adjusted to 1.6 parts by mass.
The Co and Ni ratio of the obtained product is obviously changed, and the molecular formula of the product is Co 0.4 Ni 0.6 (PO 4 ) 0.4 (OH) 0.8 ·8H 2 O。
Example 3
A method for preparing a three-shell layer hydrogen phosphate hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) The preparation of the self-sacrifice template was the same as in example 1.
(2) The layer-by-layer assembly method was similar to example 1, except that (1) the first layer was assembled, the amount of the metal nickel salt was adjusted to 3 parts by mass, (2) the second layer was assembled, the amount of the metal nickel salt was adjusted to 6.4 parts by mass, and (3) the third layer was assembled, the amount of the metal nickel salt was adjusted to 6.4 parts by mass.
The Co and Ni ratio of the obtained product is obviously changed, and the molecular formula of the product is Co 0.15 Ni 0.85 (PO 4 ) 0.4 (OH) 0.8 ·8H 2 O。
Example 4
A method for preparing a three-shell layer hydrogen phosphate hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) The preparation of the self-sacrifice template was the same as in example 1.
(2) The layer-by-layer assembly method was similar to example 1, except that (1) the first layer was assembled, the amount of sodium phosphate was adjusted to 0.5 parts by mass, and stirred at room temperature for 30 minutes; (2) assembling a second layer, adjusting the dosage of sodium phosphate to 0.8 part by mass, and stirring at room temperature for 10 minutes; (3) assembling a third layer, adjusting the dosage of sodium phosphate to 0.8 part by mass, and stirring at room temperature for 2 hours
Obtaining PO in the product 4 3- And OH (OH) - The proportion of anions is obviously changed, and the molecular formula of the product is Co 0.25 Ni 0.75 (PO 4 ) 0.2 (OH) 1.4 ·8H 2 O。
Example 5
A method for preparing a three-shell layer hydrogen phosphate hollow nano cage material by a layer-by-layer assembly method at room temperature comprises the following steps:
(1) The preparation of the self-sacrifice template was the same as in example 1.
(2) The layer-by-layer assembly method was similar to example 1, except that (1) the first layer was assembled, the amount of sodium phosphate was adjusted to 1.5 parts by mass, and stirring was performed at room temperature for 90 minutes; (2) assembling a second layer, adjusting the dosage of sodium phosphate to 3.2 parts by mass, and stirring for 30 minutes at room temperature; (3) assembling a third layer, adjusting the dosage of sodium phosphate to 3.2 parts by mass, and stirring at room temperature for 12 hours
Obtaining PO in the product 4 3- And OH (OH) - The proportion of anions is obviously changed, and the molecular formula of the product is Co 0.25 Ni 0.75 (PO 4 ) 0.5 (OH) 0.5 ·8H 2 O。
The description of the embodiments disclosed in the present invention is not intended to limit the scope of the present invention, but is used to describe the present invention. Accordingly, the scope of the invention is not limited by the above embodiments, but is defined by the claims or equivalents thereof.
Description of the drawings:
fig. 1: example 1 a schematic diagram of a three-shell layer of phosphate hydroxide hollow nanocage material is prepared by a middle layer assembly method;
fig. 2: a scanning electron microscope image of ZIF-67 obtained in example 1;
fig. 3: scanning electron microscopy images of LDH@ZIF-67 obtained in example 1;
fig. 4: a transmission electron microscope image of O-LDH@ZIF-67 obtained in example 1;
fig. 5: a transmission electron microscope image of DS-LDH@ZIF-67 obtained in example 1;
fig. 6: a transmission electron microscope image of O-DS-LDH@ZIF-67 obtained in example 1;
fig. 7: a transmission electron microscope image of TS-LDH@ZIF-67 obtained in example 1;
fig. 8: a transmission electron microscope image of TS-CNHP obtained in example 1;
fig. 9: x-ray spectrum of TS-CNHP obtained in example 1;
fig. 10: XPS map of TS-CNHP obtained in example 1;
fig. 11: TGA Pattern of TS-CNHP obtained in example 1
Fig. 12: cyclic voltammogram (a) and constant current charge-discharge diagram (b) of TS-CNHP obtained in example 1;
fig. 13: specific capacity cycle chart of TS-CNHP obtained in example 1.
Claims (4)
1. The method for preparing the three-shell layer hydrogen phosphate hollow nano cage material by the layer-by-layer assembly method at room temperature is characterized by comprising the following steps:
(1) Preparation of self-sacrifice templates: respectively dissolving 1 part by mass of cobalt nitrate hexahydrate and 0.5-2 parts by mass of dimethyl imidazole in methanol, mixing the two solutions, and standing at room temperature for 16-32 hours to obtain a ZIF-67 self-sacrifice template;
(2) Preparing a three-shell layer phosphate hydroxide hollow nano cage material by a layer-by-layer assembly method: (1) assembling a first layer, wherein 1 part by mass of ZIF-67 is dispersed in 200-1000 parts by mass of solution containing 1.2-3 parts by mass of metal nickel salt, and stirring for 30 minutes at room temperature to obtain cobalt nickel hydroxide coated ZIF-67 core-shell solution named as LDH@ZIF-67; adding 200-1000 parts by mass of aqueous solution containing 0.5-1.5 parts by mass of sodium phosphate into the solution, stirring for 30-90 minutes at room temperature, centrifuging and washing for multiple times to obtain a ZIF-67 core named O-LDH@ZIF-67 and Co-Ni LDH shell layer separation structure; (2) assembling a second layer, namely dispersing 1 part by mass of O-LDH@ZIF-67 in 500-2000 parts by mass of solution containing 1.6-6.4 parts by mass of metal nickel salt, and stirring at room temperature for 30 minutes to obtain a solution coated by two layers of nickel hydroxide shells on a new cobalt nickel hydroxide coated ZIF-67 core named DS-LDH@ZIF-67; adding 500-2000 parts by mass of aqueous solution containing 0.8-3.2 parts by mass of sodium phosphate into the solution, stirring for 10-30 minutes at room temperature, centrifuging and washing for multiple times to obtain a double-shell single-core structure in which a ZIF-67 core named O-DS-LDH@ZIF-67 is separated from an internal Co-Ni LDH shell layer; (3) assembling a third layer, namely dispersing 1 part by mass of O-LDH@ZIF-67 in 500-2000 parts by mass of solution containing 1.6-6.4 parts by mass of metal nickel salt, and stirring for 10-30 minutes at room temperature to obtain a solution coated by three layers of cobalt nickel hydroxide shells on a cobalt nickel hydroxide coated ZIF-67 core, which is named as TS-LDH@ZIF-67; adding 500-2000 parts by mass of aqueous solution containing 0.8-3.2 parts by mass of sodium phosphate into the solution, stirring for 2-12 hours at room temperature, centrifuging and washing for multiple times to obtain a phosphate hydroxide hollow nano cage material with a three-shell structure, wherein the molecular formula is Co x Ni 1-x (PO 4 ) y (OH) 2-3y Wherein x ranges from 0.15 to 0.4 and y ranges from 0.2 to 0.5.
2. The method according to claim 1, characterized in that: the metal nickel salt in the step (2) is one or more 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 according to claim 1, characterized in that: the prepared product is a hollow three-shell nano cage structure, the size of the product is 600-900nm, and the thickness of each shell is 30-80nm.
4. The use of the three-shell layer phosphate hydroxide hollow nanocage material prepared by the method of claim 1, wherein: 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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