阅读说明：本技术 一种含银镀液及泡沫金属材料的制备方法 (Silver-containing plating solution and preparation method of foam metal material ) 是由 邱业君 余靓 曾俊蓉 陈文豪 于 2020-12-29 设计创作，主要内容包括：本发明提供了一种含银镀液及泡沫金属材料的制备方法,该泡沫金属材料的制备方法包括如下步骤：步骤S1,对多孔模板进行表面处理；步骤S2,采用含银镀液对处理后的多孔模板进行镀银处理,将多孔模板浸泡于氧化液中或者将其用氧化液进行润湿,然后倾倒或滴加还原液,进行反应,得到含银多孔模板材料；或者,采用纳米银颗粒或者银纳米线的分散液,使其吸附沉积于处理后的多孔模板的表面,得到含银多孔模板材料；步骤S3,对含银多孔模板材料进行电镀,在其表面镀上一种、二种或多种金属；步骤S4,进行烧结,得到泡沫金属材料。本发明所述的制备方法具有工艺简单、成本低廉、产率高、产品形态可控、成分可调等优点。(The invention provides a silver-containing plating solution and a preparation method of a foam metal material, wherein the preparation method of the foam metal material comprises the following steps: step S1, surface treatment is carried out on the porous template; step S2, silver plating is carried out on the processed porous template by silver-containing plating solution, the porous template is soaked in oxidizing solution or is wetted by the oxidizing solution, and then reduction solution is poured or dripped for reaction to obtain silver-containing porous template material; or adopting a dispersion liquid of nano silver particles or silver nanowires to adsorb and deposit the dispersion liquid on the surface of the treated porous template to obtain the silver-containing porous template material; step S3, electroplating the silver-containing porous template material, and plating one, two or more metals on the surface of the silver-containing porous template material; and step S4, sintering to obtain the foam metal material. The preparation method has the advantages of simple process, low cost, high yield, controllable product form, adjustable components and the like.)

1. The preparation method of the foam metal material is characterized by comprising the following steps of:

step S1, surface treatment is carried out on the porous template;

step S2, silver plating is carried out on the treated porous template by silver-containing plating solution: soaking the porous template in oxidizing liquid or wetting the porous template with the oxidizing liquid, then pouring or dropwise adding reducing liquid for reaction to obtain a silver-containing porous template material; or adopting a dispersion liquid of nano silver particles or silver nanowires to adsorb and deposit the dispersion liquid on the surface of the treated porous template to obtain the silver-containing porous template material;

step S3, electroplating the silver-containing porous template material, and plating one, two or more metals on the surface of the silver-containing porous template material;

and step S4, sintering to obtain the foam metal material.

2. The method for producing a foamed metal material according to claim 1, characterized in that: step S1 includes performing surface functional group modification on the porous template by using a functional group modification solution, wherein the functional group modification solution includes an organic matter rich in amino and/or catechol groups.

3. The method for producing a foamed metal material according to claim 2, characterized in that: the functional group modification liquid comprises p-phenylenediamine, N-phenyl-p-phenylenediamine, p-phenylenediamine hydrochloride, p-phenylenediamine sulfate, 2, 5-dibromo-p-phenylenediamine, 2-chloro-1, 4-p-phenylenediamine, 2, 5-dialkynyl-p-phenylenediamine, N-diethyl-p-phenylenediamine, N-dimethyl-p-phenylenediamine, diacetyl-acetyl-p-phenylenediamine, 2-nitro-1, 4-phenylenediamine, N '-diphenyl-p-phenylenediamine, diethyl-p-phenylenediamine sulfate, 2-hydroxyethyl-p-phenylenediamine sulfate, N-methyl-p-phenylenediamine dihydrochloride, N-diethyl-p-phenylenediamine hydrochloride, N-diethyl-p-phenylenediamine sulfate, N-diethyl-p-phenylenediamine oxalate, N-cyclohexyl-N' -phenyl-p-phenylenediamine, N-, 4-aminoacetanilide, N, N-dimethyl-p-phenylenediamine monohydrochloride, N, N-dimethyl-p-phenylenediamine sulfate, N, N-dimethyl-p-phenylenediamine oxalate, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, N, N, N ', N' -tetramethyl-p-phenylenediamine radical, N, N-dimethyl-p-phenylenediamine dihydrochloride, N, N, N ', N' -tetrakis (p-aminophenyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate, N, N, N ', N' -tetramethyl-p-phenylenediamine dihydrochloride, N, N '-bis-2-naphthyl-1, 4-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, 4-aminodiphenylamine sulfate, 4-methyl-N- [4- (anilino) phenyl ] benzenesulfonamide, dopamine hydrochloride, dopamine coumarate, N-oleoyl dopamine, dopamine 3-methacrylate, DOMPERIDONE peripheral dopamine, methoxypolyethylene glycol-dopamine, 4-ethylcatechol, tris (hydroxymethyl) aminomethane hydrochloride, and tris (hydroxymethyl) aminomethane acetate.

4. The method for producing a foamed metal material according to claim 3, characterized in that: in step S3, the plating solution should include a plating solution, an anode activator, an acid-base modifier, and additives.

5. The method for producing a foamed metal material according to claim 4, characterized in that: the metal source to be plated in the metal solution to be plated comprises silver particles, silver nanowires, silver oxide particles, silver nitrate, silver acetate, silver sulfate, copper particles, copper nanowires, cuprous oxide particles, copper nitrate, copper sulfate, copper chloride, copper acetate, silver-coated copper particles, silver-copper alloy particles, copper particles, nickel particles, cobalt particles, nickel nanowires, nickel powder, nickel oxide particles, nickel nitrate, nickel acetate, nickel chloride, nickel fluoride, nickel bromide, nickel carbonate, nickel protoxide, nickel trifluoroacetate, nickel-aluminum alloy, nickel-copper alloy, cobalt acetate, cobalt phosphate, cobalt oxalate, cobalt titanate, cobaltous oxide, cobalt sulfide, cobalt bromide, cobaltous oxide, ferric sulfate, ferric oxide, ferric nitride, ferric phosphate, ferric oxalate, ferric citrate, ferrous sulfate, ferrous nitrate, ferrous powder, gold nanoparticles, gold nanowires, gold powder, gold chloroauric acid, At least one of gold bromide, gold iodide, chloroplatinic acid, platinum particles and platinum nanowires.

6. The method for producing a foamed metal material according to any one of claims 1 to 5, characterized in that: in step S4, the sintering step includes calcining at 200-1000 ℃ for 0.1-100 hours in air or oxygen atmosphere to remove the template; then pure hydrogen or H at 300-1200 DEG C₂/Ar or H₂/N₂Or H₂Calcining for 0.1-50 hours in a/He atmosphere, and reducing and sintering to obtain the foam metal material.

7. The method for producing a foamed metal material according to claim 6, characterized in that: the porous template is made of polyurethane foam, EVA sponge, melamine foam, polyethylene foam, polystyrene foam, pearl wool, phenolic foam, foamed polystyrene and polyethylene mixture foam, carbon felt or nanofiber foam material.

8. The silver-containing plating solution used in the method for producing a foamed metal material according to claim 1, wherein: the method comprises an oxidizing solution and a reducing solution, wherein the oxidizing solution comprises: silver source solution with silver ion concentration of 0.0005-10 mol/L, complexing agent with ammonium radical concentration of 0.001-50 mol/L, alkali solution with hydroxide radical concentration of 0.0001-30 mol/L and organic amine of 0.0001-250 mL/L; the volume ratio of the four solutions is silver source solution: ammonium radical solution: complexing agent: alkali solution: organic amine = 1-60%, 1-50%, 0-20%, 1-20%, 0-35%;

the reducing solution comprises the following components in concentration: 0.002-300 g/L of reducing agent, 0-250 mL/L of complexing agent and 0-100 g/L of additive.

9. The silver-containing plating solution of claim 8, wherein: the complexing agent is 0.1-300 mL/L ammonia water solution; the alkali solution comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, a glycine-sodium hydroxide buffer solution, an aluminum hydroxide solution, a cadmium hydroxide solution, a cobalt hydroxide solution, a cerium hydroxide solution, a copper hydroxide solution and a barium hydroxide solution.

10. The silver-containing plating solution of claim 8, wherein: the silver source comprises at least one of silver nanoparticles, silver nanowires, silver oxide particles, silver nitrate, silver acetate, silver sulfate thiocyanate, silver carboxyl nanoparticles, silver tetrafluoroborate, silver hexafluoroantimonate, silver bis (trifluoromethanesulfonyl) imide, silver acetylacetonate, silver lactate, silver sulfadiazine, silver trifluoroacetate, silver methanesulfonate, and silver p-toluenesulfonate;

the organic amine comprises vinyl triamine, aminoethyl piperazine, isophorone diamine, diaminocyclohexane, ethylene diamine tetraacetic acid disodium calcium, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, dipropylene triamine, dimethylamino propylamine, diethylaminopropylamine, trimethyl hexamethylene diamine, dihexyl triamine, hexamethylene diamine, trimethyl hexamethylene diamine, diethylamine, m-phenylenediamine, m-xylylenediamine, and diaminodiphenylmethane, at least one of diamino diphenyl sulfone, m-amino methylamine, benzidine, chloro-o-phenylenediamine, sulfanilamide, benzylamine, aniline, ethylamine, quinine, oleylamine, decylamine, spermine, furfurylamine, histamine, hydroxylamine, triethylamine, acetamide, ethanolamine, tert-butylamine, formamide, butyramide, trihexylamine and tripentylamine.

Technical Field

The invention belongs to the technical field of foam metal, and particularly relates to a silver-containing plating solution and a preparation method of a foam metal material.

Background

The porosity of the foam metal is generally 40-97%, and the foam metal can be roughly divided into a closed-cell structure and an open-cell structure in terms of structure. The open pore structure consists of uniform internal pores and a rigid framework, is a continuous and smooth three-dimensional pore structure, and has the advantages of high porosity, strong plasticity, high mechanical property, large surface area and the like. The unique structural characteristics enable the conductive material to show excellent conductivity, strong sound absorption and vibration reduction and electromagnetic shielding effects, and the conductive material is applied to the fields of chemical industry, aerospace, military industry and the like.

In the field of batteries, the open-cell foam metal material has a very continuous framework structure and excellent conductivity, so that the loss of a circuit is reduced, and the open-cell foam metal material is an ideal electrode reaction carrier material. In the field of catalysis, the large specific surface area of the foamed silver can increase the contact area with reactants, and meanwhile, the framework is stable, so that the better stability can be ensured, and the foamed silver is a better catalyst or catalyst carrier. The large specific surface area of the foam metal material and the high thermal conductivity of the metal elementary substance or the metal alloy material can also enhance the heat exchange efficiency, and the foam metal material is an ideal heat exchanger material. Besides, the foam metal material has wide application prospect in the aspects of building, transportation, electronic communication and the like.

At present, the manufacturing method of the foam metal mainly focuses on sintering, electroplating, alloy removing and other methods, wherein electroplating processing is a common industrial preparation process of the foam silver, and the main route is as follows: opening a porous template, conducting, chemically plating, electrodepositing, removing foam and sintering. Non-metallic materials are generally non-conductive and, in particular, catalytically inactive during electroless plating. Therefore, electrical conduction is important in the whole process. At present, the main methods include coating conductive adhesive, vacuum plating, chemical plating and the like, and a small amount of conductive metal is deposited on the surface of a porous template to trigger the chemical plating. At present, the most common sensitization activation mode is to treat the template by adopting palladium chloride and stannous chloride, but the treatment steps are complex, the price is high, and metal impurities which are difficult to remove are introduced, so that the purity of the foam metal material is reduced. Meanwhile, the conductivity of the template cannot be uniformly and highly covered by the conventional conductive treatment method, so that the adverse phenomena of collapse, shrinkage and the like can occur when the template is removed from the foam metal.

Disclosure of Invention

Aiming at the technical problems, the invention discloses a preparation method of silver-containing plating solution and a foam metal material, which solves the defects of long production process, more toxic and harmful components, environmental unfriendliness, poor preparation repeatability, high cost, large pores of a foam structure, thick framework and the like in the traditional foam metal preparation method.

In contrast, the technical scheme adopted by the invention is as follows:

a preparation method of a foam metal material comprises the following steps:

step S1, surface treatment is carried out on the porous template;

step S2, silver plating is carried out on the treated porous template by adopting the silver-containing plating solution: soaking the porous template in oxidizing liquid or wetting the porous template with the oxidizing liquid, then pouring or dropwise adding reducing liquid for reaction, so that silver is adsorbed and deposited on the surface of the treated porous template material, and the silver-containing porous template material with certain conductive performance is obtained; or adopting a dispersion liquid of nano silver particles or silver nanowires to adsorb and deposit the dispersion liquid on the surface of the treated porous template to obtain the silver-containing porous template material;

step S3, electroplating the silver-containing porous template material, and plating one, two or more metals on the surface of the silver-containing porous template material;

and step S4, sintering to obtain the foam metal material.

By adopting the technical scheme, the foam metal material made of one or more of silver, copper, nickel, cobalt, iron, gold and the like can be prepared. The preparation method of the foam metal material is the application of the silver-containing plating solution in the preparation of the foam metal material.

As a further improvement of the present invention, step S1 includes performing surface functional group modification on the porous template with a functional group modification liquid. Furthermore, organic matters rich in amino groups, catechol groups and other groups are adopted to modify the surface functional groups of the template. A large number of p-phenylenediamine groups are attached to the surface of the template, so that the attraction between silver ions in the chemical silver plating process is enhanced, and the attraction between silver ions in the chemical silver plating process is enhanced.

As a further improvement of the present invention, step S1 includes subjecting the porous template to a surface roughening treatment, which may be selectively performed according to the surface state of the template.

By adopting the technical scheme, the surface roughening and the functional group modification are sequentially carried out on the template, so that the affinity between the porous template and silver ions can be improved.

As a further improvement of the invention, in the surface treatment of the porous template, the porous template is extruded and soaked for a plurality of times, so that the contact between the template and the functional group modification liquid is promoted, and the chemical silver plating process is more uniform.

As a further improvement of the present invention, the functional group-modifying liquid comprises p-phenylenediamine, N-phenyl-p-phenylenediamine, p-phenylenediamine hydrochloride, p-phenylenediamine sulfate, 2, 5-dibromo-p-phenylenediamine, 2-chloro-1, 4-p-phenylenediamine, 2, 5-dialkynyl-p-phenylenediamine, N-diethyl-p-phenylenediamine, N-dimethyl-p-phenylenediamine, bisacetyl-p-phenylenediamine, 2-nitro-1, 4-phenylenediamine, N' -diphenyl-p-phenylenediamine, diethyl-p-phenylenediamine sulfate, 2-hydroxyethyl-p-phenylenediamine sulfate, N-methyl-p-phenylenediamine dihydrochloride, N-diethyl-p-phenylenediamine hydrochloride, N-diethyl-p-phenylenediamine sulfate, N-diethyl-p-phenylenediamine oxalate, N-diethyl-p-phenylenediamine, N, N-cyclohexyl-N '-phenyl-p-phenylenediamine, 4-aminoacetanilide, N, N-dimethyl-p-phenylenediamine monohydrochloride, N, N-dimethyl-p-phenylenediamine sulfate, N, N-dimethyl-p-phenylenediamine oxalate, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, N, N, N', N '-tetramethyl-p-phenylenediamine radical, N, N-dimethyl-p-phenylenediamine dihydrochloride, N, N, N', N '-tetrakis (p-aminophenyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate, N, N, N', N '-tetramethyl-p-phenylenediamine dihydrochloride, N, N' -di-2-naphthyl-1, 4-phenylenediamine, N, N '-di-methyl-p-phenylenediamine, N, N, N' -di-methyl-p-, At least one of N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, 4-aminodiphenylamine sulfate, 4-methyl-N- [4- (anilino) phenyl ] benzenesulfonamide, dopamine hydrochloride, dopamine coumarate, N-oleoyl dopamine, dopamine 3-methacrylate, DOMPERIDONE peripheral dopamine, methoxypolyethylene glycol-dopamine, 4-ethylcatechol, tris (hydroxymethyl) aminomethane hydrochloride, and tris (hydroxymethyl) aminomethane acetate.

As a further improvement of the present invention, in step S3, the plating solution should include a plating solution, an anode activator, an acid-base modifier, and additives.

As a further improvement of the invention, the metal-plated source in the metal-plated solution comprises silver particles, silver nanowires, silver oxide particles, silver nitrate, silver acetate, silver sulfate, copper particles, copper nanowires, cuprous oxide particles, copper nitrate, copper sulfate, copper chloride, copper acetate, silver-coated copper particles, silver-copper alloy particles, copper particles, nickel particles, cobalt particles, nickel nanowires, nickel powder, nickel oxide particles, nickel nitrate, nickel acetate, nickel chloride, nickel fluoride, nickel bromide, nickel carbonate, nickel protoxide, nickel trifluoroacetate, nickel-aluminum alloy, nickel-copper alloy, cobalt acetate, cobalt phosphate, cobalt oxalate, cobalt titanate, cobalt protoxide, cobalt sulfide, cobalt bromide, cobaltous oxide, ferric sulfate, ferric oxide, ferric nitride, ferric phosphate, ferric oxalate, ferric citrate, ferrous sulfate, ferrous nitrate, ferrous powder, gold nanoparticles, at least one of gold nano-wires, gold powder, chloroauric acid, gold bromide, gold iodide, chloroplatinic acid, platinum particles and platinum nano-wires.

As a further improvement of the present invention, in step S4, the sintering includes sequentially subjecting the material to de-templating and reduction sintering.

As a further improvement of the invention, in step S4, the sintering includes calcining at 200-1000 ℃ in an air or oxygen atmosphere for 0.1-100 hours to remove the template; then pure hydrogen or H at 300-1200 DEG C₂/Ar or H₂/N₂Or H₂Calcining for 0.1-50 hours in a/He atmosphere, and reducing and sintering to obtain the foam metal material.

As a further improvement of the present invention, the porous template may be but not limited to a non-conductive or conductive porous template such as polyurethane foam, EVA sponge, melamine foam, polyethylene foam, polystyrene foam, pearl wool, phenolic foam, expanded polystyrene polyethylene hybrid foam, carbon felt or nanofiber foam. Preferably, polyurethane foam and melamine foam are adopted, and porous materials with strong water absorption can be used as templates to increase the uniformity and success rate of chemical silvering.

As a further improvement of the invention, the foam metal material is open-cell foam, the frameworks are communicated, and the mechanical property is strong; the size of the pores of the foam metal material is 1-1000 mu m, the thickness of the framework is 1-200 mu m, and the porosity is extremely high.

The invention also discloses a silver-containing plating solution used in the preparation method of the foam metal material, which comprises an oxidizing solution and a reducing solution, wherein the oxidizing solution comprises the following components in concentration:

the oxidizing liquid includes: silver source solution with silver ion concentration of 0.0005-10 mol/L, complexing agent with ammonium radical concentration of 0.001-50 mol/L, alkali solution with hydroxide radical concentration of 0.0001-30 mol/L and organic amine of 0.0001-250 mL/L; the volume ratio of the four solutions is silver source solution: ammonium radical solution: complexing agent: alkali solution: organic amine = 1-60%, 1-50%, 0-20%, 1-20%: 0 to 35%.

The reducing solution comprises the following components in concentration: 0.002-300 g/L of reducing agent, 0-250 mL/L of complexing agent and 0-100 g/L of additive.

As a further improvement of the invention, the complexing agent is 0.1-300 mL/L ammonia water solution.

As a further improvement of the present invention, the alkali solution includes at least one of a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, a glycine-sodium hydroxide buffer solution, an aluminum hydroxide solution, a cadmium hydroxide solution, a cobalt hydroxide solution, a cerium hydroxide solution, a copper hydroxide solution, and a barium hydroxide solution. Further, the concentration of the alkali solution is 1-50 g/L.

As a further improvement of the present invention, the silver source includes at least one of silver nanoparticles, silver nanowires, silver oxide particles, silver nitrate, silver acetate, silver sulfate thiocyanate, silver carboxy nanoparticles, silver tetrafluoroborate, silver hexafluoroantimonate, silver bis (trifluoromethanesulfonyl) imide, silver acetylacetonate, silver lactate, silver sulfadiazine, silver trifluoroacetate, silver methanesulfonate, and silver p-toluenesulfonate.

As a further improvement of the invention, the organic amines include vinyl triamine, aminoethyl piperazine, isophorone diamine, diaminocyclohexane, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, calcium disodium ethylenediamine tetraacetic acid, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine, hexaethylene heptamine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, hexyldiamine, trimethylhexamethylenediamine, diethylamine, m-phenylenediamine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-aminomethane, benzidine, chlorophthaline, sulfanilamide, benzylamine, aniline, ethylamine, quinine, oleylamine, decylamine, spermine, furfurylamine, histamine, hydroxylamine, triethylamine, acetamide, ethanolamine, t-butylamine, formamide, butyramide, At least one of trihexylamine and tripentylamine.

As a further improvement of the invention, the preparation steps of the oxidizing solution comprise: under the ultrasonic condition, a silver source solution, an alkali solution and an organic amine solution are slowly dripped into a complexing agent solution in sequence.

Compared with the prior art, the invention has the beneficial effects that:

by adopting the technical scheme of the invention, the defects of long production process, more toxic and harmful components, unfriendly environment, poor preparation repeatability, high cost, large pores of a foam structure, thick framework and the like in the traditional foam metal preparation method are overcome, the preparation process has simple steps, the process is easy to control, the low cost is realized, the environmental pollution is reduced, the purity is high, the yield is high, the product form is controllable, the components are adjustable, and the preparation method has great application value in large-scale production and practical application; the silver-containing plating solution has a stable formula, can efficiently modify a template, the prepared foam metal material has high porosity and communicated frameworks, the specific surface area and the mechanical property of the foam metal material are improved, and the prepared foam metal material has a very wide application prospect in the fields of catalysis, environmental protection, wave absorption, batteries, heat conduction/heat dissipation, biology, military industry and the like.

Drawings

FIG. 1 is a schematic diagram showing the mechanism of the change process occurring during the surface treatment of the foam in example 1 of the present invention.

FIG. 2 is a SEM image of the porous template of example 1 after the completion of electroless silver plating, wherein a silver film is attached to the surface of the template. Wherein, a) is a scanning electron microscope SEM image of × 200, and b) is a scanning electron microscope SEM image of × 5k surface silver film amplification.

FIG. 3 is a SEM image of the multi-hole template of example 1 after the completion of electroplating. Wherein, a) is a scanning electron microscope SEM image of multiplied by 200, and b) is a scanning electron microscope SEM image of multiplied by 500 surface silver particles.

FIG. 4 is a SEM image of a scanning electron microscope of the silver foam of example 1 of the present invention after high temperature calcination in air to remove the template. Wherein, a) is SEM image of X50 scanning electron microscope, and b) is SEM image of X130 scanning electron microscope.

FIG. 5 is a comparison of polyurethane foam of example 1 of the present invention before and after electroless silver plating, wherein a) is a diagram of polyurethane foam before and b) is a diagram of polyurethane foam after electroless silver plating.

FIG. 6 is a SEM image of the foam silver after high-temperature sintering and reduction in example 3 of the present invention. Wherein, a) is a SEM image of a front surface of a scanning electron microscope of multiplied by 100, b) is a SEM image of a scanning electron microscope of multiplied by 250, and c) is a SEM image of an interface of a scanning electron microscope of multiplied by 1000.

Fig. 7 is a scanning electron microscope SEM image of the front surface of the silver foam obtained by using the melamine foam as the template in example 5 of the present invention.

FIG. 8 is a SEM image of a scanning electron microscope of example 6 of the present invention after deposition on the surface of the foam using silver nanowires as a silver source; wherein, a) is SEM picture of single silver nanometer x 50k scanning electron microscope, b) is SEM picture of x 15.0k of the foam surface silver-plated nano wire, and c) is SEM picture of x 1.0k of the foam surface silver-plated nano wire.

FIG. 9 is a SEM image of a scanning electron microscope of example 7 of the present invention after deposition on the surface of the foam using silver nanoparticles as a silver source; wherein, a) is SEM image of X13 k scanning electron microscope after silver particles are attached on the surface of the foam, and b) is SEM image of X500 scanning electron microscope after silver particles are attached on the surface of the foam.

FIG. 10 is a SEM image of a scanning electron microscope of Ag-Co alloy foam prepared in example 11 of the present invention at 10 k; wherein, the outmost layer is cobalt nanometer particles, and the middle layer is a silver film.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

Example 1

Preparing a high-porosity foamed silver material:

firstly, 0.1-5.0 g of potassium permanganate and 1-10 mL of concentrated sulfuric acid are dissolved in 200mL of deionized water to obtain a template surface rough solution. The polyurethane foam is extruded and soaked for 5min, and the porosity and the roughness of the material are increased.

And (3) dissolving 0.1-2 g of dopamine hydrochloride in 200mL of deionized water to obtain a functional group modification solution, and soaking the coarsened foam in the functional group modification solution for 18 hours to finish the process of modifying the surface functional groups of the foam. This step enhances the attraction of the foam surface and anions, thereby initiating the smooth progress of the electroless silver plating.

An appropriate amount of aqueous ammonia was dissolved in 50mL of deionized water to prepare an ammonia solution A. Dissolving silver salt in 30mL of deionized water to obtain a silver source solution B; and mixing A, B solution, and adding sodium hydroxide solution dropwise to adjust pH value to obtain silver-ammonia complex solution. Dissolving 8-10 g of glucose, 0.6-1.0 g of tartaric acid and 2mL of ethanol in 200mL of deionized water to obtain a reducing agent C. And soaking the foam subjected to surface modification in the last step in the silver-ammonia complexing solution, fully contacting the foam with the solution, then pouring the reducing solution C into the foam, and continuously stirring the foam to fully reduce the silver ions. After the solution became clear, indicating that the reduction process had ended, the foam was rinsed clean and dried.

The schematic mechanism of the change process in the surface treatment process of the foam is shown in fig. 1, and after the foam is subjected to functional group modification treatment, a large number of PDA groups exist on the surface of the foam, and the PDA groups provide attachment sites for silver ions in the subsequent chemical silver plating process.

After the chemical silvering, the foam surface was slightly yellow, and a relatively thin silver layer appeared on the surface of the foam fiber, and the appearance of the silver layer is shown in fig. 2.

Preparing an electroplating solution D:

s1, preparing 200mL of 200 g/L sodium thiosulfate solution;

s2, preparing 250mL of 40 g/L silver nitrate solution;

s3, preparing 250mL of 40 g/L potassium metabisulfite solution;

s4, mixing the solutions prepared in the S2 and the S3 under continuous stirring, and generating white precipitates;

s5, immediately adding the sodium thiosulfate solution prepared in the S1, continuously stirring to completely dissolve the white precipitate, and adding water to the required amount;

s6, placing the prepared plating solution under the sunlight for 2-3h, and filtering by using filter paper to obtain the clarified plating solution.

In the electroplating process, the anode electrode clamp clamps the silver sheet, the cathode clamp clamps the foam after the chemical silver plating, and the cathode current density is set to be 20 mA-cm during electroplating^-2The time can be adjusted according to the area size and the thickness of the foam. After electroplating, the foam surface turns white gray due to the attachment of a large number of silver particles, and the topography of the foam is shown in fig. 3, which shows that after electroplating, the silver particles on the template surface are tightly packed but are not sintered.

And (3) putting the electroplated foam in a muffle furnace, and calcining at 600 ℃ for 30 minutes to remove the polymer foam to obtain porous foamed silver, wherein the appearance of the porous foamed silver is shown in figure 4, and after the template is removed, silver particles on the surface of the foamed silver agglomerate but exist independently.

Example 2

Based on example 1, this example is different in that the formula of the functional group modification liquid is: 0.5-10.0 g/L of dopamine and 0.8-1.4 g/L of tris (hydroxymethyl) aminomethane. And (3) placing the template in the modification liquid, and fully extruding and soaking the template to finish the surface modification process of the template.

An appropriate amount of aqueous ammonia was dissolved in 50mL of deionized water to prepare an ammonia solution A. Dissolving silver salt in 30mL of deionized water to obtain a silver source solution B; and then mixing the AB solution, and dropwise adding a sodium hydroxide solution to adjust the pH value to obtain the silver-ammonia complex solution. Dissolving 8-10 g of glucose, 0.6-1.0 g of tartaric acid and 2mL of ethanol in 200mL of deionized water to obtain a reducing agent C. And soaking the foam subjected to surface modification in the last step in the silver-ammonia complexing solution, fully contacting the foam with the solution, then pouring the reducing solution C into the foam, and continuously stirring the foam to fully reduce the silver ions. After the solution became clear, indicating that the reduction process had ended, the foam was rinsed clean and dried. After chemical silvering, the foam surface was slightly yellow and a relatively thin silver layer was also present on the foam fiber surface.

Preparing an electroplating solution D: in accordance with example 1.

In the electroplating process, the anode electrode clamp clamps the silver sheet, the cathode clamp clamps the foam after chemical silver plating, and the electroplating time can be adjusted according to the area size and the thickness of the foam. After plating, the foam surface turned white-gray in color due to the adhesion of a large number of silver particles.

And (3) putting the electroplated foam into a muffle furnace, and calcining at 600 ℃ for 30 minutes to remove the polymer foam to obtain the porous foamed silver.

In the embodiment, the functional group modification liquid is improved, the amino group in the tris (hydroxymethyl) aminomethane has stronger activity, and the synergistic effect of the amino group and the dopamine can further enhance the acting force between the foam and silver ions, so that the chemical silver plating process is more uniform. As shown in fig. 5, which is a real image before and after the polyurethane foam is chemically plated with silver, it can be seen that the combined action of tris (hydroxymethyl) aminomethane and dopamine can modify better functional groups on the surface of the polyurethane foam, thereby greatly enhancing the attraction between the polyurethane foam and silver ions; in this embodiment, the surface modification effect of the template is stronger, so the soaking time can be reduced from 18h to 12 h.

Example 3

On the basis of embodiment 2, the present embodiment is different in that: the silver foam prepared in example 2 was placed in a tube furnace at 10% H₂Calcining in Ar atmosphere to perform a reduction sintering process. Setting the calcining temperature at 950 ℃, setting the temperature-rise rate air flow speed at 100mL/min for 1H, and stopping H after cooling to room temperature₂and/Ar gas.

After sintering, the surface of the foamed silver has metallic luster, and the appearance of the foamed silver is shown in FIG. 6. Therefore, under the reducing atmosphere, silver particles in the foamed silver are sintered, the surface is smooth, the frameworks are communicated, and silver oxide on the surface of the foamed silver is reduced into a silver simple substance, so that the purity of the foamed silver is effectively improved. Meanwhile, the silver particles are sintered more compactly at the high temperature of 950 ℃, so that the aim of high mechanical property is fulfilled.

Example 4

On the basis of example 3, the main difference of this example is the preparation of silver ammine complex solution in the electroless silver plating process: 6mL of ammonia water and 0.2mL of tetraethylenepentamine were dissolved in 50mL of deionized water to prepare an ammonia solution A. The silver salt was dissolved in 30mL of deionized water to obtain silver source solution B. And uniformly mixing the AB solution, and dropwise adding a sodium hydroxide solution to adjust the pH value to obtain the silver-ammonia complex solution. Dissolving 8-10 g of glucose, 0.6-1.0 g of tartaric acid and 2mL of ethanol in 200mL of deionized water to obtain a reducing agent C. And soaking the foam subjected to surface modification in the last step in the silver-ammonia complexing solution, fully contacting the foam with the solution, then pouring the reducing solution C into the foam, and continuously stirring the foam to fully reduce silver ions.

After the solution became clear, indicating that the reduction process had ended, the foam was rinsed clean and dried. After chemical silvering, the foam surface was slightly yellow and a relatively thin silver layer was also present on the foam fiber surface.

In the electroplating process, the anode electrode clamp clamps the silver sheet, the cathode clamp clamps the foam after chemical silver plating, and the electroplating time can be automatically adjusted according to the area size and the thickness of the foam. After plating, the foam surface turned white-gray in color due to the adhesion of a large number of silver particles.

And (3) putting the electroplated foam into a muffle furnace, and calcining at 600 ℃ for 30 minutes to remove the polymer foam to obtain the porous foamed silver. The prepared silver foam was placed in a tube furnace at 10% H₂Calcining in Ar atmosphere to perform a reduction sintering process. Setting the calcining temperature at 950 ℃, setting the temperature-rise rate air flow speed at 100mL/min for 1H, and stopping H after cooling to room temperature₂And Ar gas, thus obtaining the porous foamed silver with metallic luster.

The volume of the foam silver calcined at high temperature is basically not changed, and the thickness is always uniform, because the existence of the tetraethylenepentamine enables the silver ammine complex liquid to be more stable, the completion degree of the chemical silver plating process is higher, and the process is beneficial to the large-area chemical silver plating process.

Example 5

On the basis of embodiment 4, the present embodiment is different in that: the template is made of melamine foam with small pore diameter. The melamine foam has the advantages of good water absorption and compact pores. FIG. 7 is an SEM image of the final reduction-sintered silver foam, wherein the frameworks are connected and the pores are in the range of 50-100 microns.

Example 6

And (3) preparing foamed silver with high porosity by silver nanowire assembly.

On the basis of embodiment 4, the present embodiment is different in that: in the chemical silver plating process, the silver source in the solution is mainly silver nanowires: taking 10mL of thick silver nanowire slurry after centrifugation, uniformly mixing the thick silver nanowire slurry with an ammonia solution, and regulating and controlling the pH value of the thick silver nanowire slurry through sodium hydroxide to obtain the silver ammonia solution. After the modified porous template is completely soaked in the silver-ammonia solution, the surface of the modified foam template has a large number of PDA groups and strong affinity with silver nanowires, and the adsorption assembly process can be carried out on the surface of the foam without a reducing agent. Standing for 1 hour. After the solution becomes clear, indicating that the chemical silvering process is finished, the foam is washed and dried, and the surface of the foam has slight metallic luster.

And (4) carrying out subsequent electroplating and high-temperature treatment on the foam after the chemical silver plating is finished to obtain the foamed silver. The silver source in the chemical silver plating is silver nanowires which are good electron transmission channels, so the foamed silver prepared by the method is expected to be a high-performance battery electrode material. The SEM image of the scanning electron microscope after deposition on the foam surface, i.e. after electroless silver plating, using silver nanowires as the silver source is shown in fig. 8.

Example 7

And preparing the foamed silver with high porosity through silver nanoparticle assembly.

On the basis of embodiment 5, the present embodiment is different in that: in the chemical silver plating process, the silver source in the solution is mainly silver nanoparticles: 10mL of thick silver nanoparticle silver paste after centrifugation is taken to prepare silver ammonia solution, the surface of the modified foam template has a large number of PDA groups, strong affinity exists between the PDA groups and silver particles, and the adsorption assembly process can be carried out on the surface of the foam without a reducing agent. After the process is finished, the foam is taken out, washed and dried, and the surface of the foam has slight metallic luster, which indicates that the chemical silver plating process is finished.

At the moment, the size of the silver particles on the surface of the foam is determined by the added silver nanoparticles, so that the controllability is strong, and the method is very helpful for industrial production. Fig. 9 a) and 9 b) are SEM spectra of silver particles x 500 and x 15k, respectively, of the foam surface.

Example 8

Preparing foamed nickel with high porosity.

On the basis of embodiment 4, the present embodiment is different in that: the metal in the electroplating solution is mainly nickel, and the anode pre-plated metal sheet is a high-purity nickel sheet, so that the foamed nickel material with high porosity is prepared.

The porous template material is electroplated after surface modification and chemical silvering. The formula of the electroplating solution is as follows: 40-50 g/L boric acid, 280-400 g/L nickel sulfamate and 40-60 g/L nickel chloride solution, wherein leveling agents, brightening agents and other substances can be properly added to adjust the surface glossiness of the foamed nickel; wherein the nickel chloride can supplement nickel ions and also can be used as an anode activator.

In the electroplating process, the anode electrode clamp clamps a high-purity nickel sheet, the cathode clamp clamps the chemically silvered porous template material, and the electroplating current density is 15-80 mA/cm²The electroplating time can be adjusted according to the area size and the thickness of the foam. After plating, the foam surface turned grey due to the adhesion of a large number of nickel particles.

Sequentially placing the electroplated foam in a muffle furnace and a tubular furnace for high-temperature treatment, removing the porous template, and reducing and sintering; the temperature of the foamed nickel in the reduction sintering process in the tubular furnace can be properly adjusted within the range of 900-1200 ℃, and the porous foamed nickel is obtained.

Example 9

Preparing the foam copper with high porosity.

On the basis of embodiment 4, the present embodiment is different in that: the metal in the electroplating solution is mainly copper, and the anode pre-plated metal sheet is a high-purity copper sheet, so that the foamed copper material with high porosity is prepared.

The porous template material is electroplated after surface modification and chemical silvering. The formula of the electroplating solution is as follows: 55-105 g/L copper sulfate pentahydrate, 100-120 mL/L sulfuric acid solution, and 40-60 mg/L sodium chloride solution. The chloride ions in the sodium chloride can activate the anode and help the copper sheet to dissolve; the rate of copper deposition can be adjusted by the addition of a gloss agent or adjuvant, as appropriate.

In the electroplating process, the anode electrode clamp clamps a high-purity copper sheet, the cathode clamp clamps the chemically silvered porous template material, and the electroplating current density is 10-50 mA/cm²The plating time can be adjusted according to the area size and thickness of the foam. After electroplating, the foam surface turned reddish brown due to the adhesion of a large number of copper particles.

Sequentially placing the electroplated foam in a muffle furnace and a tubular furnace for high-temperature treatment, removing the porous template, and reducing and sintering; the temperature of the nickel foam in the reduction sintering process in the tubular furnace can be properly adjusted within the range of 700-900 ℃ to obtain the porous copper foam.

Example 10

Preparing the foamed gold with high porosity.

On the basis of embodiment 4, the present embodiment is different in that: the metal in the electroplating solution is mainly gold, and the anode pre-plated metal sheet is a gold sheet, so that the foamed copper material with high porosity is prepared.

The porous template material is electroplated after surface modification and chemical silvering. The formula of the electroplating solution is as follows: 40-50 g/L boric acid, 0.5-1.5 g/L aurous cyanide solution and 40 g/L potassium metabisulfite solution; wherein the potassium metabisulfite can function to activate the anode.

In the electroplating process, the anode electrode clamp clamps a high-purity cobalt sheet, the cathode clamp clamps the chemically silvered porous template material, and the current density is 1-10 mA/cm during electroplating^-2The time can be adjusted according to the area size and the thickness of the foam; after electroplating, the color of the foam surface is changed into yellow due to the attachment of a large amount of gold nanoparticles.

Sequentially placing the electroplated foam in a muffle furnace and a tubular furnace for high-temperature treatment, removing the porous template, and reducing and sintering; the temperature of the foam material in the reduction sintering process in the tubular furnace can be properly adjusted within the range of 900-1200 ℃, and the porous foam gold is obtained.

Example 11

Preparing the silver-cobalt alloy foam with high porosity.

On the basis of example 4, this example differs in that the electroplating is carried out in two steps, firstly the silver electroplating and secondly the cobalt electroplating, with cobalt being the predominant part. In the process of electroplating silver, the anode pre-plated metal sheet is a high-purity silver sheet, and the electroplating time is 20-30 minutes. After the surface of the foam is provided with a silver layer, replacing the electroplating solution with a cobalt-containing electroplating solution, wherein the pre-plated metal sheet is a high-purity cobalt sheet, and the formula of the electroplating solution is as follows: 40-50 g/L boric acid, 300g/L cobalt acetate solution, 40-60 g/L sodium citrate solution and 10g/L sodium hydroxide solution, and leveling agents, brightening agents and other substances can be properly added to adjust the glossiness of the surface of the foam; wherein sodium citrate is used as a reducing agent, and a sodium hydroxide solution is used as a pH regulator, so that the pH value is regulated to about 6.8.

After electroplating, the foam surface was cobalt particles and the color turned to gray. Fig. 10 shows a cross section of the silver-cobalt alloy, in which the outermost layer is cobalt nanoparticles, the middle layer is a silver film, and the cobalt particles wrap the outside of the silver film.

Sequentially placing the electroplated foam in a muffle furnace and a tubular furnace for high-temperature treatment, removing the porous template, and reducing and sintering; the temperature of the silver-cobalt alloy foam in the reducing sintering process in the tubular furnace can be properly adjusted within the range of 900-1000 ℃ to obtain the porous silver-cobalt alloy foam.

Example 12

Preparing cobalt-nickel alloy foam with high porosity.

On the basis of embodiment 4, the present embodiment is different in that: the metal in the electroplating solution is cobalt nickel, wherein nickel accounts for the main part, and the anode pre-plated metal sheet is a high-purity nickel sheet, so that the cobalt nickel alloy foam with high porosity is prepared.

The porous template material is electroplated after surface modification and chemical silvering. The formula of the electroplating solution is as follows: 40-50 g/L boric acid, 280-400 g/L nickel sulfamate, 30 g/L cobalt acetate solution and 40-60 g/L nickel chloride solution, and leveling agents, brightening agents and other substances can be properly added to adjust the surface glossiness of the foamed nickel; wherein the nickel chloride can supplement nickel ions and also can be used as an anode activator.

In the electroplating process, the anode electrode clamp clamps high-purity nickel, the cathode clamp clamps the chemically silvered porous template material, and the current density is 15-80 mA/cm during electroplating^-2The time can be adjusted according to the area size and thickness of the foam. After electroplating, the foam surface turns grey-black due to the adhesion of a large number of cobalt-nickel particles.

Sequentially placing the electroplated foam in a muffle furnace and a tubular furnace for high-temperature treatment, removing the porous template, and reducing and sintering; the temperature of the cobalt-nickel alloy foam in the reducing sintering process in the tubular furnace can be properly adjusted within the range of 900-1000 ℃ to obtain the porous cobalt-nickel alloy foam.

The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.