CN107904570A - A kind of method for preparing nickel nano particle grapheme foam nickel material - Google Patents

A kind of method for preparing nickel nano particle grapheme foam nickel material Download PDF

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Publication number
CN107904570A
CN107904570A CN201711084219.4A CN201711084219A CN107904570A CN 107904570 A CN107904570 A CN 107904570A CN 201711084219 A CN201711084219 A CN 201711084219A CN 107904570 A CN107904570 A CN 107904570A
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nickel
foam
graphene
nano particle
composite material
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CN107904570B (en
Inventor
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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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 present invention provides a kind of method for preparing nickel nano particle grapheme foam nickel composite material, mainly comprise the following steps that：1. a layer graphene is grown on nickel foam substrate with chemical vapour deposition technique (CVD), prepare grapheme foam Ni substrate, 2. using above-mentioned grapheme foam Ni substrate material as working electrode, nickel sulfate sulfuric acid mixed solution is electrolyte, galvanostatic deposition is carried out, just obtains nickel nano particle grapheme foam nickel composite material.Prepared nickel nano particle size is homogeneous, stably it is distributed in grapheme foam Ni substrate material surface, it is not easy to reunite, since nickel nano particle has preferable nano-particle activity, catalysis, sensing capabilities, big specific surface area etc., grapheme foam nickel material have good mechanical performance as basis material, electric property, chemical stability, this composite material take full advantage of the cooperative effect of the two, are being catalyzed, sensing, there is potential application prospect in the fields such as ultracapacitor, battery, Dye Adsorption.

Description

A kind of method for preparing nickel nano particle-graphene-foam nickel material
Technical field
The present invention provides a kind of method for preparing nickel nano particle-graphene-foam nickel composite material, belong to materialized Learn preparing technical field.
Background technology
Nickel nano particle has good nano-particle activity, and big specific surface area, be used to be catalyzed in recent years, passes The fields such as sense, electrochemical energy storage are used to substitute precious metal material.Graphene is due to its big specific surface area, high electric conductivity and excellent Different chemical stability becomes the ideal carrier of load nickel nano particle.Using both cooperative effects composite material is being urged Change, the field such as sensing, capacitor, battery, Dye Adsorption are exploited.Nickel nano particle-graphene composite material at present Preparation, which is focused primarily upon, modifies nickel nano particle modification in oxide-reduction method system in carbon nanotubes, or using chemical method On standby graphene, composite material prepared by these methods is existed in the form of solution, powder etc. mostly, and recycling is stranded Difficulty, or not recycling, cause the wasting of resources.We use graphene-nickel foam prepared by CVD method as basis material, Its good conductivity, mechanical performance is excellent, overcomes the drawbacks of above method is brought, and the composite material of preparation recycles easily.
During the use of nano-particle, its size, form, distribution, stability all can be to the nanocomposites Performance produces large effect.We prepare size uniformity, are evenly distributed by reasonably controlling process conditions, stability Good composite material.The material is being catalyzed, sensing, capacitor, and the field such as pollutant absorption has wide practical use.We Method technique is simple, and parameter is easy to control, cost is low, and repeatability is strong, and environmentally protective, composite material is uniform and stable.Nickel nano particle It is evenly distributed on graphene-nickel foam substrate surface to be not easy to reunite, makes full use of the cooperative effect of graphene, nickel nano particle, Prepared composite active site is more, specific surface area is big, good biocompatibility, good conductivity, catalysis, gas sensing, The fields such as Dye Adsorption, capacitor, battery have potential application prospect.
The content of the invention
Technical problem：The object of the present invention is to provide a kind of side for preparing nickel nano particle-graphene-foam nickel material Method, this method carry out permanent using the nickel foam for covering upper graphene as working electrode in the mixed solution of nickel sulfate and sulfuric acid Current deposits, prepare size and all uniform nickel nano particle of distribution.This method is without complicated processing step and variousization Learn reagent use, parameter is easy to control, cost is low, operation is simple, it is efficient, a large amount of preparations can be stablized.
Technical solution：A kind of method bag for preparing nickel nano particle-graphene-foam nickel composite material of the present invention Include following steps：
A. the cleaning of nickel foam：Nickel foam is respectively cleaned with acetone, ethanol, deionized water respectively, to remove surface oxidation Nitride layer, then use N2Drying；
B. the heat treatment of nickel foam：Nickel foam after cleaning is put into heating furnace quartz ampoule and is vacuumized, in drain Air, is passed through Ar and H2, 900 DEG C -1000 DEG C are warming up to, and anneal at this temperature；
C. graphene-nickel foam is prepared：It is passed through CH4And H2Graphene is grown, CH is disconnected after growth4, and fast cooling, etc. Heating furnace takes out sample after being cooled to room temperature, obtains covering the foam nickel material of graphene；
D. the preparation of nickel sulfate-sulfuric acid mixed solution：Nickel sulfate solution and sulfuric acid solution are prepared respectively, and sulfuric acid solution is delayed The slow nickel sulfate solution that adds uniformly is mixed；
E. the preparation of nickel nano particle-graphene-nickel foam：Using graphene-nickel foam of above-mentioned preparation as working electrode, Nickel sulfate-sulfuric acid mixed solution of above-mentioned configuration is electrolyte, carry out galvanostatic deposition, just obtain nickel nano particle-graphene- Foam nickel composite material.
Wherein：
In step b, it is 100-150sccm to be passed through Ar flows, is passed through H2Flow is 20-50sccm.
In step b, programming rate is 15 DEG C -20 DEG C/min.
In step c, CH is passed through4Flow is 10-15sccm, is passed through H2Flow is 50-100sccm.
In step d, the concentration of the nickel sulfate solution of preparation is 10-15mM, and the concentration of sulfuric acid solution is 80-100mM.
In step e, galvanostatic deposition electric current is 0.2-0.6A, sedimentation time 30-60s.
Beneficial effect：The present invention realize nickel nano particle preparation and its it is compound with graphene, it is each to give full play to its From the cooperative effect of excellent properties.The composite material uses the three-dimensional grapheme for not removing nickel foam as basis material, success Ground base metal nickel nano particle on its area load, improves the mechanical performance and stability of composite material, subtracts at the same time The use of some harmful chemical agents in material preparation process is lacked, beneficial to environmental protection.Method technique is simple, and parameter is easy Control, it is easy to operate, it is not high to technical requirements, it is easy to accomplish, environmental pollution is small, favorable repeatability, is nickel nano particle-graphite The preparation of alkene-foam nickel composite material provides a kind of effective ways.
Embodiment
The method that the present invention prepares nickel nano particle-graphene-foam nickel material is specific as follows：
CVD method prepares graphene-nickel foam：Nickel foam is used as substrate (surface density 250g1m-2, thickness 1.5mm, Size is 4-10cm2), substrate is respectively cleaned 15-20 minutes with acetone, ethanol, deionized water respectively, to remove oxide on surface Layer, then use N2Drying.It is put into heating furnace quartz ampoule and vacuumizes, the air in drain, is passed through Ar (100-150sccm) and H2 (20-50sccm), 900 DEG C -1000 DEG C are warming up to the speed of 15 DEG C -20 DEG C/min, and the 30- that anneals at this temperature 40mins.CH is passed through when growing graphene4(10-15sccm) and H2(50-100sccm), CH is disconnected after growing 5-10mins4, and Fast cooling, waits stove to take out sample after being cooled to room temperature, obtains covering the foam nickel material of graphene；
The preparation of nickel nano particle-graphene-nickel foam：Using graphene-nickel foam prepared by above-mentioned CVD method as work electricity Pole, nickel sulfate-sulfuric acid are electrolyte, carry out galvanostatic deposition, just obtain nickel nano particle-graphene-foam nickel composite material.

Claims (6)

  1. A kind of 1. method for preparing nickel nano particle-graphene-foam nickel composite material, it is characterised in that this method includes following Step：
    A. the cleaning of nickel foam：Nickel foam is cleaned with acetone, ethanol, deionized water respectively, to remove oxide layer, then Use N2Drying；
    B. the heat treatment of nickel foam：Nickel foam after cleaning is put into heating furnace quartz ampoule and is vacuumized, the air in drain, It is passed through Ar and H2, 900 DEG C -1000 DEG C are warming up to, and anneal at this temperature；
    C. graphene-nickel foam is prepared：It is passed through CH4And H2Graphene is grown, CH is disconnected after growth4, and fast cooling, wait heating Stove takes out sample after being cooled to room temperature, obtains covering the foam nickel material of graphene；
    D. the preparation of nickel sulfate-sulfuric acid mixed solution：Nickel sulfate and sulfuric acid solution are prepared respectively, then the sulfuric acid of above-mentioned preparation is molten Liquid is slowly added in nickel sulfate solution, is uniformly mixed；
    E. the preparation of nickel nano particle-graphene-nickel foam：Using the graphene of above-mentioned preparation-nickel foam substrate material as work Electrode, Pt are that Ag-AgCl is reference electrode, and the good nickel sulfate-sulfuric acid mixed solution of above-mentioned configuration is electrolyte to electrode, into Row galvanostatic deposition, with regard to nickel nano particle-graphene-foam nickel composite material can be obtained.
  2. 2. the method according to claim 1 for preparing nickel nano particle-graphene-foam nickel composite material, its feature exist In step b, it is 100-150sccm to be passed through Ar flows, is passed through H2Flow is 20-50sccm.
  3. 3. the method according to claim 1 for preparing nickel nano particle-graphene-foam nickel composite material, its feature exist In step b, the programming rate for being warming up to 900 DEG C -1000 DEG C is 15 DEG C -20 DEG C/min.
  4. 4. the method according to claim 1 for preparing nickel nano particle-graphene-foam nickel composite material, its feature exist In step c, CH is passed through4Flow is 10-15sccm, is passed through H2Flow is 50-100sccm.
  5. 5. the method according to claim 1 for preparing nickel nano particle-graphene-foam nickel composite material, its feature exist In step d, the concentration of the nickel sulfate of preparation is 10-15mM, and the concentration of sulfuric acid solution is 80-100mM.
  6. 6. the method according to claim 1 for preparing nickel nano particle-graphene-foam nickel composite material, its feature exist In step e, galvanostatic deposition electric current is 0.2-0.6A, sedimentation time 30-60s.
CN201711084219.4A 2017-11-07 2017-11-07 method for preparing nickel nanoparticle-graphene-nickel foam material Active CN107904570B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109786136A (en) * 2019-02-25 2019-05-21 天津艾克凯胜石墨烯科技有限公司 The method of Ni-Co-Mn nanoneedle is grown on a kind of 3D graphene
CN113801043A (en) * 2021-08-31 2021-12-17 浙江工业大学 Application of carbon material coated nickel nanoparticle catalyst in synthesizing m-aminobenzene sulfonic acid by hydrogenation of m-nitrobenzenesulfonic acid sodium salt
CN113823803A (en) * 2021-08-26 2021-12-21 华南理工大学 Gas diffusion layer-rGO @ Ni/Ni of proton exchange membrane fuel cellfoamPreparation method and application of
CN113828312A (en) * 2021-10-28 2021-12-24 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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109786136A (en) * 2019-02-25 2019-05-21 天津艾克凯胜石墨烯科技有限公司 The method of Ni-Co-Mn nanoneedle is grown on a kind of 3D graphene
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
CN113823803A (en) * 2021-08-26 2021-12-21 华南理工大学 Gas diffusion layer-rGO @ Ni/Ni of proton exchange membrane fuel cellfoamPreparation method and application of
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
CN113801043A (en) * 2021-08-31 2021-12-17 浙江工业大学 Application of carbon material coated nickel nanoparticle catalyst in synthesizing m-aminobenzene sulfonic acid by hydrogenation of m-nitrobenzenesulfonic acid sodium salt
CN113828312A (en) * 2021-10-28 2021-12-24 梧州学院 Preparation method of foam metal/graphene/monoatomic composite catalytic material
CN113828312B (en) * 2021-10-28 2023-11-03 梧州学院 Preparation method of foam metal/graphene/monoatomic composite catalytic material

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