CN107746459B - Nickel/cerium dioxide NP @ PANI core-shell structure composite material and preparation method thereof - Google Patents

Nickel/cerium dioxide NP @ PANI core-shell structure composite material and preparation method thereof Download PDF

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CN107746459B
CN107746459B CN201711043012.2A CN201711043012A CN107746459B CN 107746459 B CN107746459 B CN 107746459B CN 201711043012 A CN201711043012 A CN 201711043012A CN 107746459 B CN107746459 B CN 107746459B
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ceo
pani
shell structure
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CN107746459A (en
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周国伟
宫庆华
高婷婷
郑玉洁
李治凯
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Qilu University of Technology
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Abstract

The invention discloses Ni/CeO2NP @ PANI nucleusA shell structure composite material and a preparation method thereof, firstly preparing Ni/CeO by a hydrothermal method2NPs; then adopting chemical oxidation polymerization method to make Ni/CeO2The NPs polymerize aniline on the surface, and the concentration of HCl is changed during the aniline polymerization process, thereby realizing Ni/CeO2NP @ PANI core-shell structure to spaced Ni/CeO2And the NP @ PANI core-shell structure is converted into the PANI hollow sphere. In the process, a template is not needed, the environment is protected, the preparation method is simple, the preparation process is safe, the energy consumption is low, and the operability is strong. And the Ni/CeO prepared in the invention2The NPs have rough surfaces, which can increase the specific surface area and lead the Ni/CeO2The contact area between the NPs and the PANI is increased, the diffusion of ions and electrons can be promoted, and the electrochemical performance is effectively improved.

Description

Nickel/cerium dioxide NP @ PANI core-shell structure composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic/polymer composite material synthesis, and particularly relates to Ni/CeO2NP @ PANI core-shell structure composite material and a preparation method thereof.
Background
The super capacitor is a novel green energy storage element, has the advantages of long cycle life, high power density, short charging and discharging time consumption and the like, and becomes an energy storage device with a great application prospect. The conductive polymer and the metal oxide have high theoretical capacitance and are considered as main support column materials for charge storage and release of the super capacitor. Among conductive polymers, Polyaniline (PANI) has become one of the most rapidly studied conductive polymer materials due to its advantages of simple synthesis conditions, low cost, no toxicity, stable performance, etc. However, the pure PANI sample has poor cycle stability, high rigidity and poor mechanical ductility, and the redox reaction can be effectively carried out only in an acidic environment, which limits the use of the pure PANI sample in the field of supercapacitors; the metal oxide has the advantages of high theoretical specific capacitance, good electrochemical reversibility, long service life, environmental friendliness and the like. However, pure metal oxides have poor conductivity, low electrochemical utilization rate under high current, and poor rate performance.
In order to avoid the defects of different materials and prepare a supercapacitor with higher specific capacitance and better cycle stability, a conductive composite material with a synergistic effect has to be developed. In recent years, people are dedicated to the research on the compounding of conductive polyaniline and metal nano materials, because the metal/polymer nano materials integrate the characteristics of metal, polymer and nano materials, the excellent characteristics of the metal materials, conductive high molecular polymer materials and nano materials are integrated, the defects and shortcomings of the traditional single material are overcome, and the advanced material with high performance and multiple functions is obtained. The composite material not only has excellent electrochemical performance, but also can lead the conductive polyaniline to effectively carry out oxidation-reduction reaction in a neutral environment, thereby effectively expanding the application of PANI in the field of super capacitors. The compounding of the metal oxide and the PANI can generate a synergistic effect, so that the structure of the PANI is stable, and the properties of the PANI, such as specific capacitance, rate capability, cycle life and the like, are improved. Among the numerous metal oxides, CeO2As a novel inorganic material, the material has the advantages of single and unique crystal form of 4f structure, good electrochemical and optical properties and the like, and is widely applied to the fields of CO catalytic oxidation, organic synthesis catalysis, photocatalysis and the like. But CeO2The preparation of the/PANI composite material usually needs a hard template support to control the morphology, or precious metals such as Au, Ag and Pt are added to improve the performance.
For example, chinese patent application publication No. CN 106548877 a (application No. 201510609591.7) discloses a carbon nanotube array/polyaniline/ceria composite electrode, and a preparation method and application thereof, which comprises preparing a carbon nanotube array on a conductive substrate by physical or chemical vapor deposition, uniformly dispersing ceria in a hydrochloric acid solution of aniline, and finally immersing the prepared carbon nanotube array in the hydrochloric acid solution of aniline, thereby obtaining the carbon nanotube array/polyaniline/ceria composite, but the preparation method of the composite is complicated. The Chinese patent publication No. CN 102175735A (application No. 201010617684.1) discloses an AuNPs-CeO2@ PANI nano composite material, preparation method and grape made of materialGlucose biosensor. First, CeO is used2The nano particles, aniline monomer and gold nano particles (AuNPs) are compounded into AuNPs-CeO2@ PANI nano composite material, and AuNPs-CeO2And fixing glucose oxidase by using the @ PANI nano composite material to prepare the glucose biosensor. The nanocomposite does not form a controlled morphology during preparation.
Disclosure of Invention
The invention aims to overcome the defects of the traditional single material while integrating the excellent characteristics of the conductive high polymer material and the inorganic nano material, and obtain the advanced material with high performance, multiple functions and controllable appearance. The invention provides Ni/CeO2NP @ PANI core-shell structure composite material and a preparation method thereof. The nano composite material is synthesized by a two-step method, and firstly, Ni/CeO is prepared by a hydrothermal method2Nanosphere (Ni/CeO)2NPs), then adopting chemical oxidation polymerization method to make Ni/CeO2The NPs polymerize aniline on the surface, and Ni/CeO can be realized by changing the concentration of HCl in the process of polymerizing aniline2NP @ PANI core-shell structure to spaced Ni/CeO2And the NP @ PANI core-shell structure is converted into the PANI hollow sphere. The preparation method is simple, safe in preparation process, low in energy consumption, strong in operability and free of template utilization.
In order to realize the purpose, the invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided a Ni/CeO2The NP @ PANI core-shell structure composite material has the structural characteristics that: comprises CeO2The particle size of the core-shell structure is 140-200nm, the thickness of the shell layer is 20-30nm, and the diameter of the core is 0-140nm but not 0.
In a second aspect of the present invention, there is provided the above-mentioned Ni/CeO2The preparation method of the NP @ PANI core-shell structure composite material comprises the following steps:
(1)Ni/CeO2preparation of NPs:
① converting Ce (NO)3)3·6H2Adding O into ethylene glycol, and stirring to completeDissolving;
② mixing Ni (NO)3)2·6H2Adding O into the solution obtained in the step ①, and continuing stirring;
③ adding acetic acid and water into the solution obtained in step ②, and stirring to be uniform;
④, carrying out hydrothermal reaction on the solution prepared in the step ③, and cooling after the hydrothermal treatment to obtain gray precipitate;
⑤ separating the gray precipitate from ④, washing, drying, grinding, and calcining to obtain Ni/CeO2NPs with the particle size of 100-140 nm;
(2)Ni/CeO2preparation of NP @ PANI core-shell structure composite material:
① mixing Ni/CeO2NPs and polyvinylpyrrolidone (PVP) dispersed in water;
② dispersing aniline in HCl solution;
③ mixing the solution prepared in step ② and the suspension prepared in step ①;
④ Ammonium Persulfate (APS) is dissolved in water;
⑤ mixing the solution ④ with the suspension ③, and reacting;
⑥ separating, washing, drying and grinding the precipitate prepared in step ⑤ to obtain Ni/CeO2NP @ PANI core-shell structure composite material.
The sequence of the steps can be adjusted according to specific conditions.
In a third aspect of the present invention, there is provided the above-mentioned Ni/CeO2The application of the NP @ PANI core-shell structure composite material in the preparation of the super capacitor.
In a fourth aspect of the invention, a super capacitor is provided, which comprises the Ni/CeO2NP @ PANI core-shell structure composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. the HCl with different concentrations added in the invention can not only provide acidic conditions for the polymerization of aniline, but also realize Ni/CeO2NP @ PANI core-shell structure to spaced Ni/CeO2And the NP @ PANI core-shell structure is converted into the PANI hollow sphere.
2. Ni/CeO in the invention2NP @ PANI core-shell structure to spaced Ni/CeO2The conversion from the NP @ PANI core-shell structure to the PANI hollow sphere is only caused by the difference of HCl concentration added during aniline polymerization, and the preparation method is simple, safe in preparation process and high in operability.
3. The invention adopts a hydrothermal method to prepare Ni/CeO2NPs, the preparation process of this method is safe, the environmental protection is good.
4. The invention calcines Ni/CeO2The temperature used when the NPs precursor is low, the calcination time is short, and the energy consumption can be reduced.
5. Ni/CeO prepared by the invention2The NPs have rough surfaces, which can increase the specific surface area and enable the Ni/CeO2The contact area of NPs and PANI is increased; but also can promote the diffusion of ions and electrons, so that the electrochemical material has good application prospect in the field of electrochemistry.
6. Ni/CeO prepared by the invention2NP @ PANI core-shell composite to spaced Ni/CeO2The NP @ PANI core-shell structure is further converted into PANI hollow spheres, the dispersity is good, obvious aggregation is avoided, the problem that spherical PANI composite materials are prone to agglomeration is solved, the interfacial resistance in the charge transfer process is reduced, and preparation is made for further researching the electrochemical performance.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1(a) shows Ni/CeO prepared in example 1 of the present invention2Transmission Electron Micrograph (TEM) of NP @ PANI core-shell structure; (b) is Ni/CeO prepared in example 1 of the invention2Scanning Electron Micrograph (SEM) of NP @ PANI core-shell structure;
FIG. 2(a) is a schematic representation of the preparation of spaced Ni/CeO in accordance with example 2 of the present invention2Transmission Electron Micrograph (TEM) of NP @ PANI core-shell structure; (b) is the spaced Ni/CeO prepared in example 2 of the invention2NP@PANScanning Electron Microscopy (SEM) of core-shell structure I;
FIG. 3(a) is a Transmission Electron Micrograph (TEM) of PANI hollow spheres prepared in example 3 of the present invention; (b) is a Scanning Electron Microscope (SEM) image of the PANI hollow sphere prepared in the embodiment 3 of the invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, the prior art is directed to CeO2The invention provides a Ni/CeO composite material and a preparation method thereof, which have certain defects and aim to solve the technical problems2The NP @ PANI core-shell structure composite material has the structural characteristics that: comprises CeO2NPs and Ni are doped to form a spherical core and a shell made of PANI, the particle size of the core-shell structure is 140-200nm, the thickness of the shell layer is 20-30nm, and the diameter of the core is 0-140nm but is not 0.
The core-shell structure is divided into two types of interval and non-interval, the particle size of the interval core-shell structure is 140-200nm, the shell thickness is 20-30nm, and the diameter of the core is 100-140nm, which is preferably described in the embodiment 1; the particle size of the gapless core-shell structure is 140-200nm, the shell thickness is 20-30nm, the diameter of the core is 60-100nm, and the core-shell spacing is 20nm, which is preferably described in example 2.
In a preferred embodiment of the present invention, there is provided the above-mentioned Ni/CeO2Preparation method of NP @ PANI core-shell structure composite materialA method, comprising: Ni/CeO2Preparation of NPs and Ni/CeO2Preparation of NP @ PANI composite material.
In a preferred embodiment of the invention, the Ni/CeO2A method for producing NPs, comprising the steps of:
(1) adding Ce (NO)3)3·6H2Adding O into ethylene glycol, and stirring until the O is completely dissolved;
(2) mixing Ni (NO)3)2·6H2Adding O into the solution obtained in the step (1), and continuing stirring;
(3) adding acetic acid and deionized water into the solution obtained in the step (2), and stirring uniformly;
(4) transferring the solution prepared in the step (3) into a high-pressure reaction kettle, carrying out hydrothermal reaction, and cooling the high-pressure reaction kettle to room temperature after hydrothermal treatment to obtain gray precipitate;
(5) centrifuging, washing and drying the gray precipitate obtained in the step (4), grinding and calcining to obtain Ni/CeO2NPs with the particle size of 100-140 nm;
wherein, the raw material Ce (NO) is used3)3·6H2O、Ni(NO3)2·6H2O is added according to the molar ratio of 1: 0.10-0.30. When Ni/CeO2When the NPs are uniform in size, the preferred ratio is 1: 0.20.
the Ce (NO)3)3·6H2O and Ni (NO)3)2·6H2The molecular weights of O are 434.25g/mol and 290.79g/mol, respectively.
In the Ni/CeO2Among NPs, CeO thereof2Is of face-centered cubic structure.
In the step (1), the reaction temperature is 25-30 ℃, and the optimal reaction temperature is 30 ℃; the stirring time is 0.5-1h, and the optimal stirring time is 0.5 h.
In the step (2), the stirring time is 10-20min, and the optimal stirring time is 15 min.
In the step (3), the stirring time is 10-30min, and the optimal stirring time is 30 min.
In the step (4), the hydrothermal conditions are as follows: reaction is carried out for 2-4h at the temperature of 150 ℃ and 200 ℃, and the hydrothermal condition is preferably 180 ℃ for 3 h.
In the step (5), the calcination condition is 300-400 ℃ for 1-3h, and the calcination temperature is preferably 350 ℃ for 2 h.
In a preferred embodiment of the invention, the Ni/CeO2The preparation method of the NP @ PANI composite material comprises the following steps:
(1) mixing Ni/CeO2Dispersing NPs and PVP in deionized water, and performing ultrasonic dispersion;
(2) dispersing aniline in HCl solution, and stirring until the aniline is uniformly dispersed;
(3) transferring the solution prepared in the step (2) into the suspension prepared in the step (1), and stirring;
(4) dissolving Ammonium Persulfate (APS) in water;
(5) adding the solution prepared in the step (4) into the suspension obtained in the step (3), changing the solution into dark green after a period of time, and continuously stirring to obtain a precipitate;
(6) centrifuging, washing, drying and grinding the precipitate prepared in the step (5) to obtain Ni/CeO2NP @ PANI composite;
the sequence of the steps can be adjusted according to specific conditions. Wherein Ni/CeO is used2The mass ratio of the NPs to the PVP to the aniline is 1:4.0-6.0:0.5-2.0, and the preferred ratio is 1:4.0: 1.0; the molar ratio of aniline to APS is 1: 0.5-2.0, preferably in a ratio of 1: 1.0.
the molecular weights of PVP, aniline and APS are 10000.00g/mol, 93.13g/mol and 228.20g/mol respectively. In the polymerization of aniline, the addition of PVP is beneficial to the polymerization of aniline in Ni/CeO2The polymerization of the surface of the NPs can ensure that the composite material is dispersed more uniformly, and if the NPs are not added, the composite material is easy to agglomerate.
In the Ni/CeO2CeO in NP @ PANI composite material2The crystal form is not changed and still has a face-centered cubic structure.
In the step (1), the ultrasonic time is 0.5-1h, and the optimal ultrasonic time is 0.5 h.
In the step (2), the concentration of the added HCl is 0.1-10mol/L, and the optimal concentration is 1-5 mol/L.
In the step (3), stirring is carried out for 1-3h at room temperature, and the optimal reaction time is 2 h.
In the step (5), stirring is carried out for 8-24h at room temperature, and the optimal reaction time is 12 h.
In a preferred embodiment of the present invention, there is provided the above-mentioned Ni/CeO2The application of the NP @ PANI core-shell structure composite material in the preparation of the super capacitor.
In a preferred embodiment of the present invention, there is also provided a supercapacitor comprising the above-mentioned Ni/CeO2NP @ PANI core-shell structure composite material.
In the invention, the selected nickel nanoparticles have large specific surface area, high activity and special physical and chemical properties, and are widely used for conductive slurry, high-performance electrode materials and surface conductive coating treatment of metal and nonmetal, so that the nickel particles have good electrochemical performance; further, in the present invention, the loading of the metallic nickel particles is to control CeO2Morphology of (C), CeO2The regulation and control of the morphology needs the loading of noble metal nanoparticles such as Au, Ag, Pt and the like, the cost of the nickel salt is lower compared with that of the noble metal, and the results show that the successful loading and the effective regulation and control of the morphology of the composite material are nanospheres, so that the subsequent composite material with a core-shell structure can be conveniently formed; in the preparation of Ni particle-loaded CeO2In the case of nanospheres, the molar ratio of the nickel source to the cerium source and the hydrothermal temperature need to be controlled. When no nickel salt is added, CeO is obtained2Nanoparticles, rather than nanospheres; when the nickel source is too little, the nano spherical composite material can not be formed; on the other hand, too much nickel source will affect CeO2And the interaction between the polyaniline and the polyaniline is not easy to load a polyaniline shell structure, so that the performance is reduced.
The preparation of the nanocomposite of the invention is achieved by a two-step process. First, with Ce (NO)3)3·6H2O、Ni(NO3)2·6H2O is used as raw material, and Ni/CeO is synthesized by a hydrothermal method2NPs; then APS is taken as an oxidant, and the concentration of HCl is changed during aniline polymerization to realize Ni/CeO2NP @ PANI core-shell structure to spaced Ni/CeO2Conversion of NP @ PANI core-shell structure to PANI hollow sphere so as to satisfy different requirementsVarious application requirements under the circumstances.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) 0.5g of Ce (NO)3)3·6H2Adding O into 15mL of glycol, and stirring at room temperature for 0.5 h;
(2) 460. mu.L of 0.5mol/L Ni (NO)3)2·6H2Adding O into the solution obtained in the step (1), and stirring for 15min at room temperature;
(3) adding 500 mu L of acetic acid and 500 mu L of deionized water into the solution obtained in the step (2), and stirring at room temperature for 0.5 h;
(4) transferring the mixed solution obtained in the step (3) into a 20mL high-pressure reaction kettle with a polytetrafluoroethylene lining;
(5) screwing down the high-pressure reaction kettle in the step (4), putting the high-pressure reaction kettle into a drying oven, and preserving heat for 3 hours at 180 ℃; after the hydro-thermal treatment, naturally cooling the high-pressure reaction kettle to room temperature;
(6) centrifugally separating the precipitate obtained in the step (5), washing with distilled water and ethanol for 3 times respectively, drying in an air-blast drying oven at 80 ℃ for 24h, and grinding to obtain Ni/CeO2Powder;
(7) the Ni/CeO obtained in the step (6)2Calcining the powder at 350 ℃ for 2 h;
(8) the Ni/CeO obtained in the step (7)2Dispersing 20mg of powder in 25mL of deionized water, adding 100mg of PVP in an ultrasonic condition, and continuing to perform ultrasonic treatment for 0.5 h;
(9) dispersing 20 mu L of aniline in 25mL of 1mol/L HCl solution, and stirring until the aniline is uniformly dispersed;
(10) quickly adding the solution obtained in the step (9) into the suspension obtained in the step (8), and stirring at room temperature for 2 hours;
(11) dissolving 52mg APS in 20mL deionized water;
(12) adding the solution prepared in the step (11) into the suspension obtained in the step (10), and stirring at room temperature for 12 hours;
(13) centrifuging the precipitate obtained in the step (12), and washing with distilled water and ethanol respectivelyWashing for 3 times, drying at 80 deg.C for 24 hr in a forced air drying oven, and grinding to obtain Ni/CeO2NP @ PANI powder.
The Ni/CeO prepared by the method is observed by a transmission electron microscope and a scanning electron microscope, as shown in figure 1(a) and figure 1(b)2NP @ PANI core-shell composite material with the diameter of 140-200nm, Ni/CeO2The diameter of the NPs core is 100-140nm, the thickness of the PANI shell is 20-30nm, and no gap exists between the core and the shell.
Example 2
Ni/CeO2NPs were prepared by the same method as in steps (1) to (7) of example 1;
(8) the Ni/CeO obtained in the step (7)2Dispersing 20mg of powder in 25mL of deionized water, adding 100mg of PVP in an ultrasonic condition, and continuing to perform ultrasonic treatment for 0.5 h;
(9) dispersing 20 mu L of aniline in 25mL of 2mol/L HCl solution, and stirring until the aniline is uniformly dispersed;
(10) quickly adding the solution obtained in the step (9) into the suspension obtained in the step (8), and stirring at room temperature for 2 hours;
(11) dissolving 52mg APS in 20mL deionized water;
(12) adding the solution prepared in the step (11) into the suspension obtained in the step (10), and stirring at room temperature for 12 hours;
(13) centrifugally separating the precipitate obtained in the step (12), washing with distilled water and ethanol for 3 times respectively, drying in an air-blast drying oven at 80 ℃ for 24h, and grinding to obtain Ni/CeO2NP @ PANI powder.
The Ni/CeO prepared by the method is observed by a transmission electron microscope and a scanning electron microscope, as shown in FIG. 2(a) and FIG. 2(b)2In the NP @ PANI core-shell composite material, a clear interval between the core and the shell can be observed. Albeit Ni/CeO2The NPs core portion has been etched to be incomplete, but the diameter of the composite material is still in the range of 140-200nm, the thickness of the PANI shell is 20-30nm, and the core-shell spacing is about 20 nm.
Example 3
Ni/CeO2NPs were prepared by the same method as in steps (1) to (7) of example 1;
(8) the Ni/CeO obtained in the step (7)220mg of the powder was dispersed in 25mL of deionized water, 100mg of PVP was added under sonication conditions, followed byContinuing ultrasonic treatment for 0.5 h;
(9) dispersing 20 mu L of aniline in 25mL of 5mol/L HCl solution, and stirring until the aniline is uniformly dispersed;
(10) quickly adding the solution obtained in the step (9) into the suspension obtained in the step (8), and stirring at room temperature for 2 hours;
(11) dissolving 52mg APS in 20mL deionized water;
(12) adding the solution prepared in the step (11) into the suspension obtained in the step (10), and stirring at room temperature for 12 hours;
(13) and (4) centrifugally separating the precipitate obtained in the step (12), washing the precipitate with distilled water and ethanol for 3 times respectively, drying the precipitate for 24 hours at 80 ℃ in an air-blast drying oven, and grinding the dried precipitate to obtain sample powder.
Observing by transmission electron microscope and scanning electron microscope, and as shown in FIG. 3(a) and FIG. 3(b), the material prepared by the method is hollow spherical PANI, Ni/CeO2The NPs spherical core is completely etched, the diameter of the hollow spherical PANI is within the range of 140-200nm, the thickness of the PANI shell is 20-30nm, and the diameter of the cavity is about Ni/CeO2The diameter of the NPs.
Example 4
Ni/CeO2NPs were prepared by the same method as in steps (1) to (7) of example 1;
(8) the Ni/CeO obtained in the step (7)2Dispersing 20mg of powder in 25mL of deionized water, adding 100mg of PVP in an ultrasonic condition, and continuing to perform ultrasonic treatment for 0.5 h;
(9) dispersing 10 mu L of aniline in 25mL of 2mol/L HCl solution, and stirring until the aniline is uniformly dispersed;
(10) quickly adding the solution obtained in the step (9) into the suspension obtained in the step (8), and stirring at room temperature for 2 hours;
(11) dissolving 26mg of APS in 20mL of deionized water;
(12) adding the solution prepared in the step (11) into the solution obtained in the step (10), and stirring at room temperature for 12 hours;
(13) centrifugally separating the precipitate obtained in the step (12), washing with distilled water and ethanol for 3 times respectively, drying in an air-blast drying oven at 80 ℃ for 24h, and grinding to obtain Ni/CeO2NP @ PANI powder.
Example 5
Ni/CeO2NPs were prepared as in example 1The steps (1) to (7);
(8) the Ni/CeO obtained in the step (7)2Dispersing 20mg of powder in 25mL of deionized water, adding 100mg of PVP in an ultrasonic condition, and continuing to perform ultrasonic treatment for 0.5 h;
(9) dispersing 40 mu L of aniline in 25mL of 2mol/L HCl solution, and stirring until the aniline is uniformly dispersed;
(10) quickly adding the solution prepared in the step (9) into the suspension obtained in the step (8), and stirring for 2 hours at room temperature;
(11) dissolving 104mg of APS in 20mL of deionized water;
(12) adding the solution prepared in the step (11) into the suspension obtained in the step (10), and stirring at room temperature for 12 hours;
(13) centrifugally separating the precipitate obtained in the step (12), washing with distilled water and ethanol for 3 times respectively, drying in an air-blast drying oven at 80 ℃ for 24h, and grinding to obtain Ni/CeO2NP @ PANI powder.
Example 6
The electrode material of the super capacitor adopts Ni/CeO in example 12The NP @ PANI composite material is proved by experiments that the super capacitor has good application in the field of electrochemistry.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.

Claims (11)

1. Ni/CeO2The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: the method comprises the following steps:
（1）Ni/CeO2preparation of NPs:
① converting Ce (NO)3)3·6H2Adding O into ethylene glycol, and stirring until the O is completely dissolved;
② mixing Ni (NO)3)2·6H2Adding O into the solution obtained in the step ①, and continuing stirring;
③ adding acetic acid and water into the solution obtained in step ②, and stirring to be uniform;
④, carrying out hydrothermal reaction on the solution prepared in the step ③, and cooling after the hydrothermal treatment to obtain gray precipitate;
⑤ separating the gray precipitate from ④, washing, drying, grinding, and calcining to obtain Ni/CeO2NPs with the particle size of 100-140 nm;
（2）Ni/CeO2preparation of NP @ PANI core-shell structure composite material:
① mixing Ni/CeO2Ultrasonically dispersing NPs and PVP in water;
② dispersing aniline in HCl solution;
③ mixing the solution prepared in step ② and the suspension prepared in step ①;
④ Ammonium Persulfate (APS) is dissolved in water;
⑤ mixing the solution ④ with the suspension ③, and reacting;
⑥ separating, washing, drying and grinding the precipitate prepared in step ⑤ to obtain Ni/CeO2NP @ PANI core-shell structured composite; the sequence of the steps can be adjusted;
wherein, during aniline polymerization, Ni/CeO is realized by changing the concentration of HCl2NP @ PANI core-shell structure to spaced Ni/CeO2The NP @ PANI core-shell structure is converted into a PANI hollow sphere;
the Ni/CeO2NP @ PANI core-shell structure composite material comprising CeO2NPs and Ni are doped to form a spherical core and a shell made of PANI, the particle size of the core-shell structure is 140-200nm, the thickness of the shell layer is 20-30nm, and the diameter of the core is 0-140nm but is not 0.
2. The Ni/CeO of claim 12The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: the Ni/CeO2NP @ PANI core-shell structure to spaced Ni/CeO2And the conversion of the NP @ PANI core-shell structure is carried out to the conversion of the PANI hollow sphere, and the HCl concentration is 1mol/L, 2mol/L and 5mol/L respectively.
3. The Ni/CeO of claim 12The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: in the step (1), the Ce (NO) is3)3·6H2O、Ni(NO3)2·6H2The molar ratio of O is 1: 0.10-0.30;
in step ①, the reaction temperature is 25-30 ℃, and the stirring time is 0.5-1 h;
in step ②, stirring for 10-20 min;
in step ③, stirring for 10-30 min;
in the step ④, the hydrothermal condition is 150 ℃ and 200 ℃ for 2-4 h;
in step ⑤, the calcination condition is 300-400 ℃ for 1-3 h.
4. The Ni/CeO of claim 32The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: in the step (1), the Ce (NO) is3)3·6H2O、Ni(NO3)2·6H2The molar ratio of O is 1: 0.20, the reaction temperature is 30 ℃ in the step ①, the stirring time is 0.5h, the stirring time is 15min in the step ②, the stirring time is 30min in the step ③, the hydrothermal temperature is 180 ℃ in the step ④, the hydrothermal time is 3h, and the calcination temperature is 350 ℃ in the step ⑤, and the calcination time is 2 h.
5. The Ni/CeO of claim 12The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: in step (1), Ni/CeO is prepared2NPs, CeO thereof2Is of face-centered cubic structure.
6. The Ni/CeO of claim 12The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: in the step (2), the Ni/CeO2The mass ratio of NPs to PVP to aniline is 1:4.0-6.0:0.5-2.0, the molar ratio of aniline to APS is 1: 0.5-2.0.
7. The Ni/CeO of claim 62The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: in the step (2), the Ni/CeO2The mass ratio of NPs to PVP to aniline is 1:4.0: 1.0; the molar ratio of aniline to APS is 1: 1.0.
8. the Ni/CeO of claim 12The preparation method of the NP @ PANI core-shell structure composite material is characterized in that in the step (2) ①, the ultrasonic time is 0.1-1 h;
in the step (2) ②, the concentration of the added HCl is 0.1-10 mol/L;
in the step (2) ③, stirring for 1-3h at room temperature;
in the step (2) ⑤, stirring is carried out for 8-24h at room temperature.
9. The Ni/CeO of claim 82The preparation method of the NP @ PANI core-shell structure composite material is characterized in that in the step (2) ①, the ultrasonic time is 0.5h, in the step (2) ②, the concentration of HCl added is 1-5mol/L, in the step (2) ③, the stirring time at room temperature is 2h, and in the step (2) ⑤, the stirring time at room temperature is 12 h.
10. The Ni/CeO of claim 12The preparation method of the NP @ PANI core-shell structure composite material is characterized by comprising the following steps of: in step (2), prepared Ni/CeO2CeO in NP @ PANI composite material2The crystal form is not changed and still has a face-centered cubic structure.
11. The Ni/CeO of claim 12Ni/CeO prepared by preparation method of NP @ PANI core-shell structure composite material2The application of the NP @ PANI core-shell structure composite material in the preparation of the super capacitor.
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