CN107904570B - method for preparing nickel nanoparticle-graphene-nickel foam material - Google Patents

method for preparing nickel nanoparticle-graphene-nickel foam material Download PDF

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CN107904570B
CN107904570B CN201711084219.4A CN201711084219A CN107904570B CN 107904570 B CN107904570 B CN 107904570B CN 201711084219 A CN201711084219 A CN 201711084219A CN 107904570 B CN107904570 B CN 107904570B
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nickel
graphene
foam
preparing
nanoparticle
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CN107904570A (en
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郭新立
祝龙
陈忠涛
刘园园
赵丽
张伟杰
刘闯
金开
殷亮亮
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Abstract

The invention provides a method for preparing a nickel nanoparticle-graphene-nickel foam composite material, which mainly comprises the following process steps: 1. growing a layer of graphene on a foamed nickel matrix by using a Chemical Vapor Deposition (CVD) method to prepare a graphene-foamed nickel matrix, and 2, performing constant current deposition by using the graphene-foamed nickel matrix material as a working electrode and a nickel sulfate-sulfuric acid mixed solution as an electrolyte to obtain the nickel nanoparticle-graphene-foamed nickel composite material. The prepared nickel nanoparticles are uniform in size, stably distributed on the surface of the graphene-foam nickel base material and not easy to agglomerate, and the graphene-foam nickel material serving as the base material has good mechanical properties, electrical properties and chemical stability due to the fact that the nickel nanoparticles have good nanoparticle activity, catalysis and sensing properties, large specific surface area and the like, and the composite material fully utilizes the synergistic effect of the nickel nanoparticles and the graphene-foam nickel material and has potential application prospects in the fields of catalysis, sensing, supercapacitors, batteries, dye adsorption and the like.

Description

Method for preparing nickel nanoparticle-graphene-nickel foam material
Technical Field
the invention provides a method for preparing a nickel nanoparticle-graphene-nickel foam composite material, and belongs to the technical field of material chemical preparation.
Background
The nickel nanoparticles have good nanoparticle activity and large specific surface area, and are used for replacing noble metal materials in the fields of catalysis, sensing, electrochemical energy storage and the like in recent years. Graphene is an ideal carrier for supporting nickel nanoparticles due to its large specific surface area, high electrical conductivity and excellent chemical stability. The synergistic effect of the two components is utilized to develop and utilize the composite material in the fields of catalysis, sensing, capacitors, batteries, dye adsorption and the like. At present, the preparation of nickel nanoparticle-graphene composite materials is mainly focused on modifying nickel nanoparticles on carbon nanotubes or modifying graphene prepared by an oxidation reduction method by using a chemical method, and most of the composite materials prepared by the methods exist in the forms of solution, powder and the like, so that the composite materials are difficult to recycle or are not recycled, and the resource waste is caused. The graphene-nickel foam prepared by the CVD method is used as a matrix material, so that the graphene-nickel foam composite material has good conductivity and excellent mechanical property, overcomes the defects caused by the method, and is easy to recycle.
In the using process of the nano particles, the size, the shape, the distribution and the stability of the nano particles can generate great influence on the performance of the nano composite material. By reasonably controlling the process conditions, the composite material with uniform size, uniform distribution and good stability is prepared. The material has wide application prospect in the fields of catalysis, sensing, capacitors, pollutant adsorption and the like. The method has the advantages of simple process, easy parameter control, low cost, strong repeatability, environmental protection and uniform and stable composite material. The nickel nano particles are uniformly distributed on the surface of the graphene-foam nickel base and are not easy to agglomerate, the synergistic effect of the graphene and the nickel nano particles is fully utilized, and the prepared composite material has the advantages of multiple active sites, large specific surface area, good biocompatibility and good conductivity, and has potential application prospects in the fields of catalysis, gas sensing, dye adsorption, capacitors, batteries and the like.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a method for preparing a nickel nanoparticle-graphene-nickel foam material, which takes the nickel foam covered with graphene as a working electrode, and carries out constant current deposition in a mixed solution of nickel sulfate and sulfuric acid to prepare the nickel nanoparticles with uniform size and distribution. The method has the advantages of no complicated process steps and use of various chemical reagents, easily controllable parameters, low cost, simple and easy operation, high efficiency and stable mass preparation.
The technical scheme is as follows: the method for preparing the nickel nanoparticle-graphene-nickel foam composite material comprises the following steps of:
a. cleaning the foamed nickel, namely respectively cleaning the foamed nickel by using acetone, ethanol and deionized water to remove a surface oxide layer, and then drying by using N 2;
b. heat treatment of foamed nickel, which is to put the cleaned foamed nickel into a quartz tube of a heating furnace for vacuumizing, remove the air in the tube, introduce Ar and H 2, heat up to 900-1000 ℃ and anneal at the temperature;
c. Preparing graphene-nickel foam, namely introducing CH 4 and H 2 to grow graphene, cutting CH 4 after the graphene grows, quickly cooling the graphene, and taking out a sample after a heating furnace is cooled to room temperature to obtain a graphene-covered nickel foam material;
d. Preparing a nickel sulfate-sulfuric acid mixed solution: respectively preparing a nickel sulfate solution and a sulfuric acid solution, slowly adding the sulfuric acid solution into the nickel sulfate solution, and uniformly mixing;
e. Preparing nickel nano particles-graphene-foamed nickel: and (3) taking the prepared graphene-foamed nickel as a working electrode and the prepared nickel sulfate-sulfuric acid mixed solution as an electrolyte, and carrying out constant current deposition to obtain the nickel nanoparticle-graphene-foamed nickel composite material.
Wherein:
In step b, the flow rate of Ar is 100-150sccm, and the flow rate of H 2 is 20-50 sccm.
In the step b, the temperature rising speed is 15-20 ℃/min.
in the step c, the CH 4 is introduced at a flow rate of 10-15sccm, and the H 2 is introduced at a flow rate of 50-100 sccm.
In the step d, the concentration of the prepared nickel sulfate solution is 10-15mM, and the concentration of the prepared sulfuric acid solution is 80-100 mM.
In the step e, the constant current deposition current is 0.2-0.6A, and the deposition time is 30-60 s.
Has the advantages that: the preparation method realizes the preparation of the nickel nano particles and the compounding of the nickel nano particles and the graphene, and fully exerts the synergistic effect of the excellent performances of the nickel nano particles and the graphene. The composite material adopts three-dimensional graphene without foam nickel as a base material, and non-noble metal nickel nano particles are successfully loaded on the surface of the three-dimensional graphene, so that the mechanical property and the stability of the composite material are improved, and the use of some harmful chemical reagents in the material preparation process is reduced, thereby being beneficial to environmental protection. The method has the advantages of simple process, easily controlled parameters, convenient operation, low technical requirement, easy realization, small environmental pollution and good repeatability, and provides an effective method for preparing the nickel nanoparticle-graphene-nickel foam composite material.
Detailed Description
The method for preparing the nickel nanoparticle-graphene-nickel foam material comprises the following steps:
Preparing graphene-foam nickel by a CVD (chemical vapor deposition) method, namely taking foam nickel as a substrate (the surface density is 250g 1 m -2, the thickness is 1.5mm, and the size is 4-10cm 2), respectively cleaning the substrate for 15-20 minutes by using acetone, ethanol and deionized water to remove a surface oxide layer, then drying the substrate by using N 2, putting the substrate into a heating furnace quartz tube for vacuumizing, removing air in the tube, introducing Ar (100-150sccm) and H 2 (20-50sccm), heating the tube to 900-1000 ℃ at the speed of 15-20 ℃/min, annealing the tube at the temperature for 30-40mins, introducing CH 4 (10-15sccm) and H 2 (50-100sccm) when growing graphene, cutting off CH 4 after growing for 5-10mins, rapidly cooling the furnace to room temperature, and taking out a sample to obtain a foam nickel material covering the graphene;
Preparing nickel nano particles-graphene-foamed nickel: and (3) taking the graphene-foamed nickel prepared by the CVD method as a working electrode and taking nickel sulfate-sulfuric acid as electrolyte, and carrying out constant current deposition to obtain the nickel nanoparticle-graphene-foamed nickel composite material.

Claims (2)

1. a method for preparing a nickel nanoparticle-graphene-nickel foam composite material is characterized by comprising the following steps:
a. Cleaning the foamed nickel, namely cleaning the foamed nickel by using acetone, ethanol and deionized water respectively to remove a surface oxide layer, and then drying by using N 2;
b. heat treatment of foamed nickel, which is to put the cleaned foamed nickel into a quartz tube of a heating furnace for vacuumizing, remove the air in the tube, introduce Ar and H 2, heat up to 900-1000 ℃ and anneal at the temperature;
c. Preparing graphene-nickel foam, namely introducing CH 4 and H 2 to grow graphene, cutting CH 4 after the graphene grows, quickly cooling the graphene, and taking out a sample after a heating furnace is cooled to room temperature to obtain a graphene-covered nickel foam material;
d. Preparing a nickel sulfate-sulfuric acid mixed solution: respectively preparing nickel sulfate and a sulfuric acid solution, slowly adding the prepared sulfuric acid solution into the nickel sulfate solution, and uniformly mixing;
e. preparing nickel nano particles-graphene-foamed nickel: taking the prepared graphene-foam nickel matrix material as a working electrode, Pt as a counter electrode, Ag-AgCl as a reference electrode, and the prepared nickel sulfate-sulfuric acid mixed solution as an electrolyte, and carrying out constant current deposition to obtain a nickel nanoparticle-graphene-foam nickel composite material;
in the step b, the flow rate of Ar is 100-150sccm, and the flow rate of H 2 is 20-50 sccm;
In the step c, CH 4 is introduced at a flow rate of 10-15sccm, and H 2 is introduced at a flow rate of 50-100 sccm;
in the step d, the concentration of the prepared nickel sulfate is 10-15mM, and the concentration of the sulfuric acid solution is 80-100 mM;
In the step e, the constant current deposition current is 0.2-0.6A, and the deposition time is 30-60 s.
2. The method for preparing a nickel nanoparticle-graphene-nickel foam composite material according to claim 1, wherein in the step b, the temperature rise rate of the temperature rise to 900 ℃ to 1000 ℃ is 15 ℃ to 20 ℃/min.
CN201711084219.4A 2017-11-07 2017-11-07 method for preparing nickel nanoparticle-graphene-nickel foam material Active CN107904570B (en)

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CN109786136B (en) * 2019-02-25 2021-10-08 天津艾克凯胜石墨烯科技有限公司 Method for growing Ni-Co-Mn nanoneedle on 3D graphene
CN113823803B (en) * 2021-08-26 2023-04-18 华南理工大学 Proton exchange membrane fuel cell gas diffusion layer-rGO @ Ni/Ni foam Preparation method and application of
CN113801043B (en) * 2021-08-31 2022-10-11 浙江工业大学 Application of carbon material coated nickel nanoparticle catalyst in synthesis of m-aminobenzene sulfonic acid by hydrogenation of m-nitrobenzenesulfonic acid sodium salt
CN113828312B (en) * 2021-10-28 2023-11-03 梧州学院 Preparation method of foam metal/graphene/monoatomic composite catalytic material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105671515A (en) * 2016-03-24 2016-06-15 东南大学 Simple preparation method of gold nanoparticle/three-dimensional graphene/foamed nickel composite structure
CN106676875A (en) * 2016-12-26 2017-05-17 浙江大学 Graphene-nickel composite fiber and preparation method thereof
CN106994347A (en) * 2017-03-27 2017-08-01 东南大学 A kind of method for preparing square copper nano-particle grapheme foam nickel material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105671515A (en) * 2016-03-24 2016-06-15 东南大学 Simple preparation method of gold nanoparticle/three-dimensional graphene/foamed nickel composite structure
CN106676875A (en) * 2016-12-26 2017-05-17 浙江大学 Graphene-nickel composite fiber and preparation method thereof
CN106994347A (en) * 2017-03-27 2017-08-01 东南大学 A kind of method for preparing square copper nano-particle grapheme foam nickel material

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