CN108436100B - Preparation method of ultrathin porous nano nickel foil - Google Patents
Preparation method of ultrathin porous nano nickel foil Download PDFInfo
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- CN108436100B CN108436100B CN201810320654.0A CN201810320654A CN108436100B CN 108436100 B CN108436100 B CN 108436100B CN 201810320654 A CN201810320654 A CN 201810320654A CN 108436100 B CN108436100 B CN 108436100B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011888 foil Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 5
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000012798 spherical particle Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002932 luster Substances 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000011232 storage material Substances 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005452 bending Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0551—Flake form nanoparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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Abstract
The patent provides a preparation method of ultrathin porous nano nickel foil, which adopts Ni2+And trisodium citrate or a mixed aqueous solution of ascorbic acid, chloroplatinic acid or chloroauric acid is used as a precursor solution, hydrazine hydrate is used as a reducing agent, and the ultrathin porous nano nickel foil is prepared under specific conditions. The nickel foil is attached to the wall of the beaker, is formed by self-assembling and arranging spherical particles with the diameter of about 300-400 nm, is porous, has the thickness of only the diameter of a single nickel particle, has the excellent performances of good conductivity, light weight and bending, and can be matched with different substrates to be used in the fields of sensors, electrode materials, storage materials, electromagnetic shielding materials and the like. The preparation method has the advantages of simple preparation process, short time consumption and low cost, and can meet the requirement of large-scale production.
Description
The technical field is as follows:
the invention relates to the technical field of preparation of nano materials, in particular to a preparation method of an ultrathin porous nano nickel foil.
Background
The nickel foil is one of the basic materials for electronics, telecommunication, instruments and other industries, is commonly used for electromagnetic shielding, high-energy-storage-density alkaline storage batteries, surface resistance and other applications, and can be used as a novel fireproof, moistureproof and antimagnetic packaging material after being processed. In recent years, nickel foils have been developed to thinner and smaller microstructures due to the industry's demand for some special-purpose metallic materials. On one hand, the ultrathin nickel foil can reduce materials, lighten the mass, improve the flexibility and increase the specific surface area; on the other hand, the porous nano array on the surface of the nickel foil provides active sites and a huge surface area, which is beneficial to further functionalization, so that the nickel foil becomes an excellent composite material carrier. The ultra-thin porous nano nickel foil has received wide attention from researchers due to excellent physical and chemical properties.
Most of the existing nickel foil preparation methods are carbonyl methods or electrolytic methods, but all have great defects.
For example, CN1110726A discloses a process for producing nickel foil by electrodeposition to electrolyzeThe nickel is used as an anode, the rotatable titanium roller is used as a cathode, and electrolytic deposition is carried out under the rotation of the cathode. The electrolyte contains NiSO4·7H2O240-360 g/L of NiCl2·6H2O8-40 g/l, H3BO330-45 g/l, and the pH value of the electrolyte is 1.8-3.4. The electrolyte overflows from the electrolytic bath, is subjected to electrolytic purification and preheating, then enters the electrolytic bath, and is controlled to flow at a certain rate for closed cycle. The nickel foil prepared by the method has larger particle size which is micron-sized, and the electrolyte used by the method has toxicity and pollutes the environment, thereby increasing the waste liquid treatment cost.
CN103031578A discloses an electrolysis method for producing nickel foil, which comprises using a lead silver plate or a titanium plate as an anode, using a titanium roller or a stainless steel roller which can rotate and control the rotating speed as a cathode, controlling the distance between the cathode and the anode at 9-15 mm, circulating an electrolyte consisting of 200-300 g/L nickel sulfate and 40-45 g/L boric acid and having a pH value of 1.7-3.5 into an electrolytic cell, switching on the power supply of the electrolytic cell and controlling the voltage to enable the cathode current density to be 21-35A/dm2And controlling the temperature of the electrolyte at 50-60 ℃, rotating the titanium roller or the stainless steel roller at a constant speed, continuously rotating the titanium roller or the stainless steel roller to strip out the nickel foil electrolytically deposited on the titanium roller or the stainless steel roller, washing, drying and coiling the obtained nickel foil to form a continuously coiled nickel foil, namely the produced product. The preparation process of the method needs to be controlled in the whole process, the prepared nickel foil is thick, the particle size is large, and the electrolyte used by the method has toxicity and pollutes the environment.
CN102995085A discloses a method for producing a roughened nickel foil by an electrolytic method, which is applied to the field of electrolytic production of nickel foils. It comprises the following steps: the method comprises the following steps: selecting a semi-bright nickel foil as a base material of the coarsened nickel foil, and carrying out activation treatment on the semi-bright nickel foil; step two: placing the activated semi-bright nickel foil in the first step into a roughening electrolytic tank consisting of 18-25 g/L nickel sulfate and 21-23 g/L ammonium sulfate, electrifying the cathode and the anode of the roughening electrolytic tank, and roughening the roughening electrolytic tank; step three: placing the nickel foil subjected to the roughening treatment in the step two in a solidification electrolytic tank of a solution consisting of 200 g/L-250 g/L of nickel sulfate, 40-45 g/L of boric acid and 40g/L of nickel chloride, electrifying a cathode and an anode of the solidification electrolytic tank, and carrying out solidification treatment; step four: and (5) drying the nickel foil subjected to the curing treatment in the third step. The method has the advantages of complex preparation process, high energy consumption, large particle size of the prepared nickel foil, toxicity of the electrolyte used by the method, environmental pollution and increased waste liquid treatment cost.
Although the carbonylation method has high productivity and meets the industrial demand, the carbonylation process has high requirements on production processes and equipment and is easy to cause toxic gas leakage, thereby causing serious environmental pollution. Although the electrolytic method has simple equipment, the production process is complex and is easily influenced by environmental factors, the energy consumption is high, and the productivity is low. In addition, the preparation methods do not have special ultrathin porous nano structures, so the method has important significance for meeting the requirements of special applications, improving the productivity and reducing the energy consumption.
Disclosure of Invention
Aiming at the defects in the prior art, the invention firstly provides a method for preparing the ultrathin porous nano nickel foil in a water bath. The basic principle is that nano nickel formed by reaction is arranged on the wall of a beaker in a self-assembly manner to form a single-layer porous nano nickel foil. The method has simple operation, high productivity and low cost.
The invention discloses a method for preparing an ultrathin porous nano nickel foil in a water bath, which comprises the following steps:
step S1: preparation of Ni-containing2+The precursor solution-A solution of (1) is specifically Ni2+Mixing trisodium citrate or ascorbic acid, chloroplatinic acid or chloroauric acid in water solution and stirring to mix evenly;
step S2: preparation of reducing liquid-liquid B, i.e. hydrazine hydrate (NH)4·H2O) an aqueous solution;
step S3: adjusting the pH values of the solution A and the solution B by using sodium hydroxide;
step S4: pouring the solution B into a beaker filled with the solution A, and then heating the solution B in water bath at 70-90 ℃ for 15 min-1 h;
step S5: and cooling after the reaction is finished, taking out the nickel foil growing on the wall of the beaker, washing the nickel foil with absolute ethyl alcohol, and then putting the nickel foil into a vacuum drying oven for drying treatment.
Preferably, the Ni2+One or more selected from nickel chloride, nickel sulfate, nickel nitrate and nickel acetate; ni in solution2 +The concentration range of the compound is 0.01-2M, the concentration range of trisodium citrate or ascorbic acid is 0.01-2M, and the concentration range of chloroplatinic acid or chloroauric acid is 0.01-5 mM. The concentration range of each substance is selected by combining continuous trial and grope in the experimental process according to theoretical calculation such as the amount of each substance in the oxidation-reduction reaction, the excess principle of the reducing agent, the growth principle of the seed crystal and the like.
Preferably, the concentration range of hydrazine hydrate in the hydrazine hydrate aqueous solution is 0.01-1M. The preference is based on the excess of the reducing agent, which ensures that the material is not wasted and the reaction is fully carried out.
Preferably, the volume ratio of the liquid A to the liquid B is 1: 1. The preferred mixing of solution A and solution B in the next step provides a mild and stable environment.
Preferably, the concentration range of the sodium hydroxide in the pH value adjusting process is 0.01-1M. The preferred hydrazine hydrate provides an alkaline environment at a pH of about 12 to facilitate the hydrazine hydrate's ability to exert its reducing properties and to better conduct the redox reaction.
Preferably, the reaction temperature of the solution A and the solution B after mixing is 80 ℃, and the reaction time is 30 min. This preference ensures sufficient reaction in a short time, and gives an ideal nickel foil.
Another object of the present invention is to provide an ultra-thin porous nano nickel foil prepared by the foregoing preparation method.
The nickel foil is flat and clean in surface, has metal luster, is formed by self-assembling and arranging spherical particles with the diameter of about 300-400 nm, is porous, and has the thickness of single-layer nano nickel particles.
The nickel foil has excellent conductivity and magnetism, and can be matched with different substrates to be used in the fields of sensors, electrode materials, storage materials, electromagnetic shielding materials and the like.
The invention also provides the ultrathin porous nano nickel foil growing on the substrate in situ, different substrates (such as filter paper, fabrics, ITO substrates and the like) are stuck and fixed on the wall of the beaker, and the ultrathin porous nano nickel foil prepared by the preparation method grows on the substrate in situ.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method has the advantages of simple preparation process, short time consumption, high production efficiency and low cost, and can meet the requirement of large-scale production.
2. The ultrathin porous nano nickel foil produced by the invention has the thickness (about 500nm) of single-layer nano nickel particles, greatly reduces the mass, improves the flexibility, increases the specific surface area and can meet certain special application requirements.
3. The ultrathin porous nano nickel foil produced by the invention has a porous nano structure, provides an active site and a huge surface area, and is beneficial to further functionalization, so that the ultrathin porous nano nickel foil becomes an excellent composite material carrier.
4. The invention can grow ultrathin porous nano nickel foil in situ on different substrates (such as filter paper, fabric, ITO substrate and the like) to directly obtain the conductive and magnetic flexible substrate, thereby realizing the application in the field of wearable equipment.
5. The ultrathin porous nano nickel foil produced by the invention has excellent conductivity and magnetism, and can be matched with different substrates to be used in the fields of sensors, electrode materials, storage materials, electromagnetic shielding materials and the like.
Description of the drawings:
FIG. 1 is a diagram of an ultra-thin porous nano-nickel foil attached to the wall of a beaker in accordance with the present invention.
FIG. 2 is an XRD pattern of the ultrathin porous nano nickel foil in the invention.
FIG. 3 is an SEM image of an ultrathin porous nano nickel foil in accordance with the present invention; wherein 3(a) is a plan view of the nickel foil and 3(b) is a sheet view of the nickel foil.
Wherein:
as can be seen from FIG. 2, the material corresponds exactly to the standard PDF card of Ni, which is a face centered cubic crystal structure.
As shown in FIG. 3(a), the prepared nickel foil is formed by self-assembling and arranging spherical particles with the diameter of about 300-400 nm and is porous; as can be seen from fig. 3(b), the nickel foil has a thickness of a single layer of nano nickel particles (about 500 nm).
The specific implementation mode is as follows:
the invention is further illustrated, but not limited, by the following examples and figures.
Example 1:
the preparation method of the ultrathin porous nano nickel foil comprises the following steps:
(1) preparation of Ni-containing2+Precursor liquid (liquid a): 1.1g of nickel chloride, 5.6mg of chloroplatinic acid and 1.8g of trisodium citrate were weighed into 30mL of deionized water, and mixed well with stirring.
(2) Preparation of reducing solution (solution B): weighing 4mL of hydrazine hydrate (40-50%) and adding the hydrazine hydrate into 26mL of deionized water, and stirring and mixing the mixture uniformly.
(3) Preparation of aqueous sodium hydroxide solution: 0.4g NaOH was weighed into 40mL deionized water and mixed well with stirring.
(4) 20mL of aqueous sodium hydroxide solution was added to solution A and solution B, respectively, and the mixture was stirred and mixed well.
(5) Pouring the solution B into a beaker filled with the solution A, and then heating in a water bath at 80 ℃ for 15 min.
(6) And cooling after the reaction is finished, taking out the nickel foil growing on the wall of the beaker, washing with water and absolute ethyl alcohol, and then putting into a vacuum drying oven for drying treatment.
The ultrathin porous nano nickel foil obtained by the implementation has a smooth and clean surface and metallic luster, the diameter of nano nickel particles is about 300-400 nm, and the thickness of the nickel foil is about 500 nm.
As shown in figure 1, an ultra-thin porous nano nickel foil is attached to the wall of the beaker. XRD of the ultrathin porous nano nickel foil is shown in figure 2, and SEM image of the ultrathin porous nano nickel foil is shown in figure 3; wherein 3(a) is a plan view of the nickel foil and 3(b) is a sheet view of the nickel foil.
As can be seen from FIG. 2, the material corresponds exactly to the standard PDF card of Ni, which is a face centered cubic crystal structure.
As shown in FIG. 3(a), the prepared nickel foil is formed by self-assembling and arranging spherical particles with the diameter of about 300-400 nm and is porous; as can be seen from fig. 3(b), the nickel foil has a thickness of a single layer of nano nickel particles (about 500 nm).
Example 2:
the method for in-situ growth of the ultrathin porous nano nickel foil on the substrate comprises the following steps:
the same procedure as in example 1 was followed except that a substrate (chemical fiber fabric) of a certain size was fixed to the wall of the beaker containing the solution A with an adhesive tape and the heating time in the water bath was prolonged to 1 hour.
The ultrathin porous nano nickel foil growing on the substrate in situ is obtained, the diameter of nano nickel particles is about 300-400 nm, and the thickness of the nickel foil is about 400 nm.
Example 3:
the method for in-situ growth of the ultrathin porous nano nickel foil on the substrate comprises the following steps:
preparation of Ni-containing2+The amount of chloroplatinic acid in the precursor solution (solution A) was increased ten times (0.056g), and the procedure was as in example 2.
The ultrathin porous nano nickel foil growing on the substrate in situ is obtained, the diameter of nano nickel particles is about 200-300 nm, and the thickness of the nickel foil is about 300 nm.
Example 4 Performance testing
The performance detection method and the result are as follows:
the results show that the ultrathin porous nano nickel foil produced by the invention is composed of nickel particles with smaller sizes in self-assembly arrangement, can be of a single-layer ultrathin structure, has excellent conductivity and magnetism, and can be matched with different substrates to be used in the fields of sensors, electrode materials, storage materials, electromagnetic shielding materials and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A method for in-situ growth of ultrathin porous nano nickel foil on a substrate, comprising the steps of:
step S1: preparation of Ni-containing2+The precursor solution-A solution of (1) is specifically Ni2+Mixing with trisodium citrate or ascorbic acid, chloroplatinic acid or chloroauric acid, stirring, and mixing to obtain Ni2+One or more selected from nickel chloride, nickel sulfate, nickel nitrate and nickel acetate; and Ni in the mixed aqueous solution2+The concentration range of the compound is 0.01-2M, the concentration range of trisodium citrate or ascorbic acid is 0.01-2M, and the concentration range of chloroplatinic acid or chloroauric acid is 0.01-5 mM;
step S2: preparing a reducing solution-B solution, namely a hydrazine hydrate aqueous solution, wherein the concentration range of the hydrazine hydrate is 0.01-1M;
step S3: adjusting the pH values of the solution A and the solution B by using sodium hydroxide, wherein the concentration of the sodium hydroxide is 0.01-1M, and the pH value is adjusted to 12;
step S4: pasting and fixing different substrates on the wall of a beaker, wherein the substrate is one of filter paper, fabric or ITO, pouring the solution B into the beaker filled with the solution A, and then heating the solution in water bath for 1h at 70-90 ℃ to enable the ultrathin porous nano nickel foil to grow in situ on the substrate;
step S5: cooling after the reaction is finished, taking out the substrate on which the nickel foil grows on the wall of the beaker, washing and drying;
the nickel foil is flat and clean in surface, has metal luster, is formed by self-assembling and arranging spherical particles with the diameter of 300-400 nm, is porous, and has the thickness of single-layer nano nickel particles.
2. The method for in-situ growth of ultra-thin porous nano nickel foil on a substrate according to claim 1, wherein the cooling after the reaction is finished means that the beaker is taken out after the reaction is finished for 1 hour and is naturally cooled to room temperature.
3. An ultra-thin porous nano nickel foil obtained by the method of growing an ultra-thin porous nano nickel foil in situ on a substrate according to any one of claims 1 to 2.
4. The ultra-thin porous nano-nickel foil according to claim 3, wherein the nickel foil is applicable in the fields of sensors, electrode materials, memory materials, electromagnetic shielding materials, wearable devices.
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