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CN-121983433-A - Three-dimensional multilayer LDH/CS/PPy composite material and preparation method and application thereof

CN121983433ACN 121983433 ACN121983433 ACN 121983433ACN-121983433-A

Abstract

The invention discloses a three-dimensional multilayer LDH/CS/PPy composite material, a preparation method and application thereof, wherein the composite material has a multilayer core-shell structure, a carbon sphere CS with a surface rich in functional groups is used as a structure guide core, nickel cobalt aluminum layered double metal hydroxide NiCoAl-LDH is induced to grow on the surface of the composite material in situ to form a uniformly dispersed flower-shaped structure, a polypyrrole PPy conducting layer is coated on the surface of the composite material by an in-situ polymerization method to construct a three-dimensional conducting network, and the composite material is applied to the assembly of an asymmetric supercapacitor (LDH/CS/PPy// AC) and has ultrahigh power density and energy density, can lighten a plurality of parallel LEDs, and can be used for constructing a novel supercapacitor with high energy density, high power density and excellent cycle stability.

Inventors

  • LI CHUNYAN

Assignees

  • 江苏科技大学

Dates

Publication Date
20260505
Application Date
20260209

Claims (10)

  1. 1. The three-dimensional multi-layer LDH/CS/PPy composite material is characterized by having a multi-layer core-shell structure, taking a carbon sphere CS with a surface rich in functional groups as a structure guiding core, inducing the nickel cobalt aluminum layered double metal hydroxide NiCoAl-LDH to grow on the surface of the composite material in situ to form a uniformly dispersed flower-shaped structure, and coating a polypyrrole PPy conductive layer on the surface of the composite material by an in-situ polymerization method to construct a three-dimensional conductive network.
  2. 2. A method of preparing a three-dimensional, multi-layered LDH/CS/PPy composite material according to claim 1, comprising the steps of: (1) Dissolving citric acid and urea in deionized water, stirring to form a uniform solution, performing hydrothermal reaction, dialyzing and purifying the product after the reaction is finished, and performing centrifugal separation and drying treatment to obtain the nano carbon sphere material with the surface rich in functional groups; (2) Mixing nickel salt, cobalt salt, aluminum salt and ammonium fluoride, dissolving urea to prepare a precipitator solution, mixing the two solutions, performing hydrothermal reaction, washing and drying a reaction product to obtain nickel cobalt aluminum layered double hydroxide NiCoAl-LDH; (3) Adding the carbon sphere material obtained in the step (1) into the metal salt solution of NiCoAl-LDH obtained in the step (2), fully dispersing, mixing with urea solution, and carrying out hydrothermal reaction to enable the layered double hydroxide to grow on the surface of the carbon sphere in situ, so as to obtain an LDH/CS composite material with tightly combined carbon sphere and layered double hydroxide; (4) Uniformly dispersing the composite material obtained in the step (3) in an aqueous solution, adding pyrrole monomers and a surfactant, adding an initiator solution prepared from an oxidant and hydrochloric acid after full dispersion, carrying out in-situ chemical oxidative polymerization, and washing and drying a product after the reaction is finished to obtain the three-dimensional multi-layer LDH/CS/PPy composite material.
  3. 3. The preparation method according to claim 2, wherein in the step (1), the mass ratio of citric acid to urea is 7:5-7, the reaction kettle is heated for 4-5 hours at 160-180 ℃, and the supernatant is taken out for drying in the dialysis process.
  4. 4. The method according to claim 2, wherein in the step (2), the molar ratio of nickel salt, cobalt salt, aluminum salt, ammonium fluoride and urea is 1-2:2-3:1.5:16:19.2.
  5. 5. The preparation method according to claim 2, wherein in the step (2), the urea solution is rapidly poured into the metal salt solution, and the hydrothermal reaction is performed at 110 to 120 ℃ for 5 to 6 hours.
  6. 6. The preparation method of claim 2, wherein in the step (3), the mass-volume ratio of the carbon sphere material, the NiCoAl-LDH and the urea solution is 1-5:16.3:38.4.
  7. 7. The method according to claim 2, wherein in the step (3), CS is 1-5 mg mL -1 , and the hydrothermal reaction is carried out at 110-120 ℃ for 5-6 hours.
  8. 8. The preparation method of claim 2, wherein in the step (4), the mass-to-volume ratio of the LDH/CS composite material, the pyrrole monomer, the oxidant and the hydrochloric acid is 1:0.15-3.5:0.9:8.5, the surfactant is cetyl trimethyl ammonium bromide, and the oxidant is ammonium persulfate.
  9. 9. Use of a three-dimensional multi-layered LDH/CS/PPy composite material according to claim 1 as an electrode material in the technical field of energy material preparation.
  10. 10. The use according to claim 9, wherein the prepared LDH/CS/PPy composite electrode material is applied to anode materials of high performance supercapacitors, and the asymmetric supercapacitors are assembled with LDH/CS/PPy as positive electrode and AC as negative electrode.

Description

Three-dimensional multilayer LDH/CS/PPy composite material and preparation method and application thereof Technical Field The invention relates to a three-dimensional multilayer LDH/CS/PPy composite material, and also relates to a preparation method of the composite material and application of the composite material serving as an electrode material in the technical field of energy material preparation. Background The super capacitor is used as a novel electrochemical energy storage device, and has the advantages of high power density, rapid charging and discharging capability, long cycle life and the like, and has wide application prospect in the field of energy storage. Its core energy storage mechanism involves electric double layer adsorption at the electrode surface and redox reactions occurring in the active material. Thus, the performance of the electrode material directly determines the energy storage efficiency, stability and economy of the supercapacitor system. Layered Double Hydroxides (LDHs) are typical anionic layered materials whose unique interlayer structure allows efficient charge storage by ion exchange or redox reactions. In theory, the electrode material is an ideal electrode material of the supercapacitor, but the practical application of the electrode material is limited by two major bottlenecks, namely, the stacking agglomeration is easy to cause due to stronger van der Waals force between LDH layers, so that active sites cannot be fully exposed, and the poor conductivity of the electrode material causes low electron transmission efficiency, so that the energy storage performance and the cycling stability are difficult to meet the practical requirements. Therefore, how to break through the performance limitation of LDH-based materials through structural design and component regulation and control becomes a problem to be solved in the field of supercapacitors. Disclosure of Invention The invention aims to provide a three-dimensional multilayer LDH/CS/PPy composite material, and also provides a preparation method of the composite material and application of the composite material serving as an electrode material in the technical field of energy material preparation. According to the technical scheme, the three-dimensional multi-layer LDH/CS/PPy composite material has a multi-layer core-shell structure, a carbon sphere CS with a surface rich in functional groups is used as a structure guiding core, nickel cobalt aluminum layered double metal hydroxide NiCoAl-LDH is induced to grow on the surface of the composite material in situ to form a uniformly dispersed flower-shaped structure, and a polypyrrole PPy conducting layer is coated on the surface of the composite material through an in-situ polymerization method to construct a three-dimensional conducting network. The preparation method of the three-dimensional multilayer LDH/CS/PPy composite material comprises the following steps: (1) Dissolving citric acid and urea in deionized water, stirring to form a uniform solution, performing hydrothermal reaction, dialyzing and purifying the product after the reaction is finished, and performing centrifugal separation and drying treatment to obtain the nano carbon sphere material with the surface rich in functional groups; (2) Mixing nickel salt, cobalt salt, aluminum salt and ammonium fluoride, dissolving urea to prepare a precipitator solution, mixing the two solutions, performing hydrothermal reaction, washing and drying a reaction product to obtain nickel cobalt aluminum layered double hydroxide NiCoAl-LDH; (3) Adding the carbon sphere material obtained in the step (1) into the metal salt solution of NiCoAl-LDH obtained in the step (2), fully dispersing, mixing with urea solution, and carrying out hydrothermal reaction to enable the layered double hydroxide to grow on the surface of the carbon sphere in situ, so as to obtain an LDH/CS composite material with tightly combined carbon sphere and layered double hydroxide; (4) Uniformly dispersing the composite material obtained in the step (3) in an aqueous solution, adding pyrrole monomers and a surfactant, adding an initiator solution prepared from an oxidant and hydrochloric acid after full dispersion, carrying out in-situ chemical oxidative polymerization, and washing and drying a product after the reaction is finished to obtain the three-dimensional multi-layer LDH/CS/PPy composite material. In the step (1), the mass ratio of citric acid to urea is 7:5-7, the reaction kettle is heated for 4-5 hours at 160-180 ℃, and the supernatant is taken in the dialysis process and dried. In the step (2), the mass ratio of nickel salt to cobalt salt to aluminum salt to ammonium fluoride to urea is 1-2:2-3:1.5:16:19.2, and the urea solution is rapidly poured into the metal salt solution and heated for 5-6 hours at the temperature of 110-120 ℃ in a hydrothermal reaction. In the step (3), the mass-volume ratio of the carbon sphere material to the NiCoAl-LDH