WO2024099479A2 - 梯度润湿铜镍多层复合材料及其制备方法与应用 - Google Patents

梯度润湿铜镍多层复合材料及其制备方法与应用 Download PDF

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WO2024099479A2
WO2024099479A2 PCT/CN2024/071832 CN2024071832W WO2024099479A2 WO 2024099479 A2 WO2024099479 A2 WO 2024099479A2 CN 2024071832 W CN2024071832 W CN 2024071832W WO 2024099479 A2 WO2024099479 A2 WO 2024099479A2
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Prior art keywords
copper
nickel
foam block
metal foam
composite material
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PCT/CN2024/071832
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English (en)
French (fr)
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WO2024099479A3 (zh
Inventor
朱丽静
曾志翔
马付良
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中国科学院宁波材料技术与工程研究所
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Publication of WO2024099479A2 publication Critical patent/WO2024099479A2/zh
Publication of WO2024099479A3 publication Critical patent/WO2024099479A3/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/138—Water desalination using renewable energy
    • Y02A20/142—Solar thermal; Photovoltaics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/208—Off-grid powered water treatment
    • Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation

Definitions

  • the present application relates to a composite material, and in particular to a gradient wetting copper-nickel multilayer composite material and a preparation method and application thereof, belonging to the technical field of functional materials.
  • Metal foam is a new type of three-dimensional porous material with the advantages of high porosity, large specific surface area, and good mechanical strength. It has strong application potential as an adsorption material, filter material, heat dissipation material, etc. in sewage treatment, photothermal desalination and other fields.
  • Photothermal desalination uses heat energy converted from solar energy to obtain clean water from seawater and sewage, and is a promising water purification technology to solve the shortage of clean water resources.
  • metal foam materials In the field of photothermal desalination, metal foam materials have high thermal conductivity and can quickly convert solar energy into thermal energy, promote the rapid evaporation of water molecules, and improve the desalination capacity of seawater.
  • hydrophilic metal foam when hydrophilic metal foam is directly used for photothermal desalination, inorganic salts in seawater are transferred to the photothermal evaporation layer along with water molecules. After the water evaporates, the inorganic salts will be deposited and hardened on the surface of the photothermal conversion material, reducing the photothermal conversion rate. In addition, metal foams are prone to corrosion when used in high-salt environments, reducing the mechanical stability and service life of photothermal conversion materials.
  • the main purpose of the present application is to provide a gradient wetting copper-nickel multilayer composite material to overcome the deficiencies in the prior art.
  • Another object of the present application is to provide a method for preparing a corresponding gradient wetting copper-nickel multilayer composite material.
  • Another object of the present application is to provide an application of the gradient wetting copper-nickel multilayer composite material.
  • An embodiment of the present application provides a gradient wetting copper-nickel multilayer composite material, which includes a metal foam block wrapped in a super-hydrophilic copper-nickel coating, a hydrophobic polyolefin salt-blocking and anti-corrosion layer, and a hydrophobic photothermal evaporation layer with a micro-nano structure, which are sequentially stacked in the thickness direction.
  • the present application also provides a method for preparing a gradient wetting copper-nickel multilayer composite material, which comprises:
  • the metal foam block is used as a first anode, and the first anode, the first cathode and the sulfur-containing nickel electroplating solution are used to form a first electrochemical working system; the first electrochemical working system is energized to perform a first electrodeposition reaction, and a sulfur-containing nickel plating layer is deposited on the metal foam block to obtain a metal foam block wrapped with the sulfur-containing nickel plating layer;
  • the present application also provides a gradient wetting copper-nickel multilayer composite material prepared by the aforementioned method.
  • the embodiments of the present application also provide the application of the aforementioned gradient wetting copper-nickel multilayer composite material in the fields of photothermal seawater desalination or photothermal wastewater purification.
  • the functional layers of the gradient wettability copper-nickel multilayer composite material provided in the present application complement each other to form a bottom-up gradient wettability multilayer composite material, which can be used in the field of photothermal seawater desalination/photothermal sewage purification;
  • the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer of the present application has high porosity and good hydrophilicity, which can quickly supply water molecules to the photothermal evaporation layer; and has good mechanical strength and excellent chemical stability, which makes the composite material have a long life;
  • the hydrophobic polyolefin salt-blocking and anti-corrosion layer of the present application can prevent excess water from being transferred to the photothermal evaporation layer, effectively preventing the formation of a water film on the photothermal evaporation layer and the loss of light and heat, and inhibiting the accumulation of salt in the photothermal evaporation layer and reducing the corrosion of salt on the metal foam block wrapped by the super-hydrophilic copper-nickel coating;
  • the hydrophobic photothermal evaporation layer of the present application contains nanomaterials with micro-nano structures, which have strong light absorption and photothermal conversion capabilities.
  • the functional layers complement each other and are multifunctionally coupled to obtain a high-performance composite material with gradient wetting properties.
  • FIG1 is a schematic diagram of the structure of a gradient wetting copper-nickel multilayer composite material in a typical embodiment of the present application
  • FIG2 is a SEM image of the upper surface of the gradient wetting copper-nickel multilayer composite material prepared in Example 3 of the present application;
  • FIG3 is a picture of the contact angle between the upper surface of the gradient wetting copper-nickel multilayer composite material and water prepared in Example 3 of the present application;
  • FIG4 is a picture of the contact angle between the lower surface of the gradient wetting copper-nickel multilayer composite material prepared in Example 3 of the present application and water.
  • a gradient wetting copper-nickel multilayer composite material as shown in Figure 1, which includes a metal foam block 1 wrapped with a super-hydrophilic copper-nickel coating, a hydrophobic polyolefin salt-blocking and anti-corrosion layer 2, and a hydrophobic photothermal evaporation layer 3 with a micro-nano structure, which are stacked in sequence in the thickness direction.
  • the gradient wetting copper-nickel multilayer composite material includes three layers from bottom to top, namely a metal foam block 1 wrapped by a super-hydrophilic copper-nickel coating, and a hydrophobic polyolefin salt-blocking and anti-corrosion layer 2 and a hydrophobic photothermal evaporation layer 3 with a micro-nano structure sequentially covering the metal foam block 1 wrapped by the super-hydrophilic copper-nickel coating.
  • the metal foam block wrapped by the super-hydrophilic copper-nickel coating has high porosity and good hydrophilicity, which quickly supplies water molecules to the photothermal evaporation layer; and has good mechanical strength and excellent chemical stability, so that the composite material has a long service life;
  • the hydrophobic polyolefin salt-blocking and anti-corrosion layer prevents excess water from being transmitted to the photothermal evaporation layer, effectively preventing the formation of a water film on the photothermal evaporation layer and the loss of light and heat, and inhibiting the accumulation of salt in the photothermal evaporation layer;
  • the hydrophobic photothermal evaporation layer contains nanomaterials with micro-nano structures, which have strong light absorption and photothermal conversion capabilities.
  • a method for preparing a gradient wetting copper-nickel multilayer composite material which mainly utilizes electrochemical technology to wrap a super hydrophilic copper-nickel coating on a metal foam skeleton to improve its resistance to seawater corrosion and seawater transmission rate; then constructs an ultra-thin hydrophobic polyolefin salt-blocking and anti-corrosion layer to solve the problems of salting out and hardening; finally, constructs a hydrophobic photothermal evaporation layer containing micro-nanostructured nanomaterials to improve light absorption and photothermal conversion capabilities.
  • the method for preparing the gradient wetting copper-nickel multilayer composite material comprises the following steps:
  • the metal foam block is used as a first anode, and the first anode, the first cathode and the sulfur-containing nickel electroplating solution are used to form a first electrochemical working system; the first electrochemical working system is energized to perform a first electrodeposition reaction, and a sulfur-containing nickel plating layer is deposited on the metal foam block to obtain a metal foam block wrapped with the sulfur-containing nickel plating layer;
  • the sulfur-containing nickel electroplating solution includes 5-25 wt % nickel salt, 1-5 wt % sulfur-containing organic matter, 0.05-11 wt % complexing agent and 0.01-3 wt % surfactant.
  • the nickel salt includes any one or a combination of two of nickel sulfate and nickel chloride, but is not limited thereto.
  • the sulfur-containing organic matter includes any one or a combination of two or more of benzenesulfonic acid, ethylenethiourea and benzoylsulfonimide, but is not limited thereto.
  • the complexing agent includes any one of boric acid and citric acid or a combination of two thereof, but is not limited thereto.
  • the surfactant includes any one or a combination of two or more of sodium lauryl sulfate, behenyltrimethylammonium chloride and sodium ethylhexyl sulfate, but is not limited thereto.
  • the material of the metal foam block includes at least one of nickel and copper.
  • the process conditions of the first electrodeposition reaction include: a current density of 1 to 10 A/dm 2 , a temperature of 30 to 60° C., and a time of 1 to 100 h.
  • the first cathode may be a nickel sheet, but is not limited thereto.
  • the copper electroplating solution includes 10-30 wt % copper salt, 1-10 wt % acid and 0.5-10 wt % inorganic salt.
  • the copper salt includes any one or a combination of two of copper sulfate and copper chloride, but is not limited thereto.
  • the acid includes any one of sulfuric acid and hydrochloric acid or a combination of two thereof, but is not limited thereto.
  • the inorganic salt includes any one or a combination of two of sodium chloride and potassium chloride, but is not limited thereto.
  • the process conditions of the second electrodeposition reaction include: a current density of 0.5 to 10 A/dm 2 , a temperature of 30 to 60° C., and a time of 0.1 to 2 h.
  • the sintering temperature is 200 to 600° C. and the sintering time is 0.5 to 24 hours.
  • the second cathode may be a copper sheet, but is not limited thereto.
  • the porous copper plating layer has a pore size of 0.01 to 100 ⁇ m and a porosity of 10 to 90%.
  • step (3) specifically comprises:
  • Low-temperature plasma technology is used to deposit a hydrophobic polyolefin salt-blocking and anti-corrosion layer on a metal foam block wrapped with a super-hydrophilic copper-nickel coating to obtain a gradient wetting metal foam block; wherein the helium flow rate is 100-200sccm, the flow rate of the olefin gas is 10-100sccm, the pressure is 10-1000mToor, the duty cycle is 10%-100%, the power is 40-80W, and the reaction time is 10-180min.
  • the olefin gas may include any one or a combination of two or more of ethylene, propylene, vinyl chloride, etc., but is not limited thereto.
  • step (4) specifically comprises:
  • the gradient wetting metal foam block is immersed in water, and taken out after soaking for 10 to 30 minutes; then immersed in a mixed solution consisting of 0.1 to 10 wt% nanomaterial, 0.1 to 10 wt% bismuth iodide micron particles, 0.1 to 10 wt% PDMS, 0.01 to 2 wt% curing agent and organic solvent, and taken out after soaking for 1 to 30 minutes; finally, thermally cured at 50 to 120° C. for 10 to 300 minutes to generate a hydrophobic photothermal evaporation layer with a micro-nano structure.
  • the particle size of the bismuth oxyiodide microparticles is 0.1 to 5 ⁇ m.
  • the nanomaterial includes at least one of zero-dimensional nanoparticles, two-dimensional reduced graphene oxide and one-dimensional carbon nanotubes, forming a micro-nano structure, i.e., a multi-level structure.
  • the nanomaterial includes any one or a combination of two or more of ferroferric oxide nanoparticles with a particle size of 10 to 100 nm, reduced graphene oxide with a diameter of 100 nm to 5 ⁇ m and 1 to 8 layers, and carbon nanotubes with a diameter of 2 to 50 nm, but is not limited thereto.
  • the organic solvent may include any one or a combination of two or more of chloroform, n-hexane, and ethyl acetate, but is not limited thereto.
  • the preparation method of the gradient wetting copper-nickel multilayer composite material may include the following steps:
  • step 1 Immersing the pretreated metal foam block and the nickel sheet in the sulfur-containing nickel electroplating solution A in step 1 to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; connecting a power supply, applying a reduction current with a current density of 1 to 10 A/ dm2 between the anode and the cathode, and performing an electroplating reaction at 30 to 60°C for 1 to 100 hours to obtain a metal foam block coated with a sulfur-containing nickel coating;
  • the sulfur-containing nickel electroplating solution A comprises 5 to 25 wt% of a nickel salt, 1 to 5 wt% of a sulfur-containing organic matter, 0.05 to 11 wt% of a complexing agent, and 0.01 to 3 wt% of a surfactant;
  • the invention relates to an electrochemical working system in which a metal foam block wrapped with a sulfur-containing nickel coating is used as an anode and a copper sheet is used as a cathode; a power source is connected, and a reduction current with a current density of 0.5 to 10 A/ dm2 is applied between the anode and the cathode, and an electrodeposition reaction is performed at 30 to 60°C for 0.1 to 2 hours to generate a porous copper coating; and then the metal foam block wrapped with a super-hydrophilic copper-nickel coating is obtained after sintering at 200 to 600°C; the copper electroplating solution B comprises 10 to 30 wt% of a copper salt, 1 to 10 wt% of an acid, and 0.5 to 10 wt% of an inorganic salt;
  • step (3) immersing the gradient wetting metal foam block prepared in step (3) in water, taking it out after immersion for 10 to 30 minutes, and brushing off excess water; then immersing it in a mixed solution consisting of 0.1 to 10 wt% nanomaterial, 0.1 to 10 wt% bismuth iodide micron particles, 0.1 to 10 wt% PDMS, 0.01 to 2 wt% curing agent and organic solvent, taking it out after immersion for 1 to 30 minutes, and thermally curing it at 50 to 120° C.
  • a mixed solution consisting of 0.1 to 10 wt% nanomaterial, 0.1 to 10 wt% bismuth iodide micron particles, 0.1 to 10 wt% PDMS, 0.01 to 2 wt% curing agent and organic solvent, taking it out after immersion for 1 to 30 minutes, and thermally curing it at 50 to 120° C.
  • the particle size of the bismuth iodide micron particles is 0.1 to 5 ⁇ m;
  • the nanomaterial includes any one or a combination of two or more of ferroferric oxide nanoparticles with a particle size of 10 to 100 nm, reduced graphene oxide with a diameter of 100 nm to 5 ⁇ m and 1 to 8 layers, and carbon nanotubes with a diameter of 2 to 50 nm.
  • the present application uses a metal foam block as a carrier, and electroplates a superhydrophilic copper-nickel coating on the carrier layer through electrodeposition technology, and then uses low-temperature plasma technology to deposit a hydrophobic polyolefin salt-blocking and anti-corrosion layer on the metal foam block wrapped by the superhydrophilic copper-nickel coating.
  • a hydrophobic photothermal evaporation layer with a micro-nano structure is prepared by solution dip coating.
  • the functional layers complement each other to form a three-layer composite material with gradient wettability from bottom to top, which can be used in the field of photothermal seawater desalination/photothermal sewage purification.
  • the gradient wetting copper-nickel multilayer composite material includes a metal foam block wrapped in a super-hydrophilic copper-nickel coating, a hydrophobic polyolefin salt-blocking and anti-corrosion layer, and a hydrophobic photothermal evaporation layer with a micro-nano structure, which are sequentially stacked in the thickness direction.
  • the super-hydrophilic copper-nickel plating layer has a thickness of 0.1 to 300 ⁇ m and a porosity of 50 to 85%.
  • the thickness of the hydrophobic polyolefin salt-blocking and anti-corrosion layer is 0.05 to 50 ⁇ m.
  • the hydrophobic photothermal evaporation layer having a micro-nano structure has a thickness of 0.1 to 800 ⁇ m.
  • the contact angle between the upper surface of the gradient wetting copper-nickel multilayer composite material and water is 151-157°, and the contact angle between the lower surface and water is 151-157°.
  • the contact angle with water is 0°.
  • the water evaporation rate is 2.5-2.9 kg m -2 h -1
  • the photothermal conversion efficiency is 91-95%.
  • Another aspect of the embodiments of the present application also provides the application of the aforementioned gradient wetting copper-nickel multilayer composite material in the fields of photothermal seawater desalination or photothermal wastewater purification.
  • the functional layers of the gradient wettability copper-nickel multilayer composite material provided by the present application complement each other to form a bottom-up gradient wettability multilayer composite material, which can be used in the field of photothermal seawater desalination/photothermal sewage purification.
  • step 1 (1) immersing the pretreated nickel foam block and nickel sheet into the sulfur-containing nickel electroplating solution A in step 1 to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; connecting the power supply, applying a reduction current with a current density of 1A/ dm2 between the anode and the cathode, and performing an electroplating reaction at 30°C for 100 hours to obtain a metal foam block wrapped with a sulfur-containing nickel coating;
  • the sulfur-containing nickel electroplating solution A comprises 5wt% nickel sulfate, 1wt% benzenesulfonic acid, 0.05wt% boric acid and 0.01wt% sodium dodecyl sulfate;
  • the copper electroplating solution B comprises 10 wt% copper sulfate, 1 wt% sulfuric acid, and 0.5 wt% sodium chloride;
  • a hydrophobic polyethylene salt barrier and anti-corrosion layer is deposited on a metal foam block wrapped with a super-hydrophilic copper-nickel coating to obtain a gradient wetting metal foam block; wherein the helium gas flow rate is 100 sccm, the ethylene gas flow rate is 10 sccm, the pressure is 10 mToor, the duty cycle is 10%, the power is 40 W, and the reaction time is 180 minutes;
  • step (3) Immerse the gradient wetting nickel foam block prepared in step (3) in water, take it out after soaking for 10 minutes, and wipe off excess water; then immerse it in a mixed solution consisting of 0.1wt% ferrosoferric oxide nanoparticles (particle size is 10nm), 10wt% bismuth iodide micron particles (particle size is 0.1 ⁇ m), 0.1wt% PDMS, 0.01wt% curing agent and chloroform, soak it for 30 minutes and take it out, and heat cure it at 50°C for 10 minutes to generate a hydrophobic photothermal evaporation layer with a micro-nano structure.
  • a mixed solution consisting of 0.1wt% ferrosoferric oxide nanoparticles (particle size is 10nm), 10wt% bismuth iodide micron particles (particle size is 0.1 ⁇ m), 0.1wt% PDMS, 0.01wt% curing agent and chloroform, soak it for 30 minutes and take
  • the water contact angle of the upper surface of the composite material prepared in this embodiment is 152°, and the water contact angle of the lower surface is 0°; under the condition of simulated sunlight, the water evaporation rate is 2.5 kg m -2 h -1 , and the photothermal conversion efficiency is 91%.
  • the sulfur-containing nickel electroplating solution A comprises 25wt% nickel chloride, 5wt% ethylene thiourea, 11wt% citric acid and 3wt% docosyltrimethylammonium chloride;
  • the copper electroplating solution B comprises 30wt% of cupric chloride, 10wt% of hydrochloric acid, and 10wt% of potassium chloride;
  • a hydrophobic polyvinyl chloride salt-blocking and anti-corrosion layer is deposited on a metal foam block wrapped with a super-hydrophilic copper-nickel coating to obtain a gradient wetting metal foam block; wherein the helium gas flow rate is 200 sccm, the vinyl chloride gas flow rate is 100 sccm, the pressure is 1000 mToor, the duty cycle is 100%, the power is 80 W, and the reaction time is 10 minutes;
  • the gradient wetting copper foam block prepared in step (3) is immersed in water, taken out after soaking for 30 minutes, and excess water is wiped off; then immersed in a mixed solution consisting of 10wt% reduced graphene oxide (diameter 100nm, number of layers 1), 0.1wt% iodine bismuth oxide micron particles (particle size 5 ⁇ m), 10wt% PDMS, 2wt% curing agent and ethyl acetate, taken out after soaking for 1 minute, and thermally cured at 120°C for 300 minutes to generate a hydrophobic photothermal evaporation layer with a micro-nano structure.
  • a mixed solution consisting of 10wt% reduced graphene oxide (diameter 100nm, number of layers 1), 0.1wt% iodine bismuth oxide micron particles (particle size 5 ⁇ m), 10wt% PDMS, 2wt% curing agent and ethyl acetate, taken out after soaking for 1 minute
  • the water contact angle of the upper surface of the composite material prepared in this embodiment is 157°, and the water contact angle of the lower surface is 0°; under the condition of simulated sunlight, the water evaporation rate is 2.8 kg m -2 h -1 and the photothermal conversion efficiency is 94%.
  • the copper electroplating solution B comprises 15wt% copper sulfate, 5wt% sulfuric acid, and 4wt% sodium chloride;
  • a hydrophobic polypropylene salt-blocking and anti-corrosion layer is deposited on a metal foam block wrapped with a super-hydrophilic copper-nickel coating to obtain a gradient wetting metal foam block; wherein the helium gas flow rate is 150 sccm, the propylene gas flow rate is 40 sccm, the pressure is 600 mToor, the duty cycle is 60%, the power is 60 W, and the reaction time is 90 minutes;
  • the gradient wetting copper foam block prepared in step (3) was immersed in water, taken out after immersion for 20 minutes, and excess water was wiped off; then immersed in a mixed solution consisting of 2wt% carbon nanotubes (diameter 2nm), 2wt% bismuth iodide particles (particle size 2 ⁇ m), 2wt% PDMS, 0.03wt% curing agent and chloroform, and taken out after immersion for 15 minutes, and thermally cured at 80°C for 120 minutes to generate a hydrophobic photothermal evaporation layer with a micro-nano structure.
  • the water contact angle of the upper surface of the composite material prepared in this embodiment is 151°, and the water contact angle of the lower surface is 0°; under the condition of simulated sunlight, the water evaporation rate is 2.9 kg m -2 h -1 , and the photothermal conversion efficiency is 95%.
  • the copper electroplating solution B comprises 15wt% copper sulfate, 5wt% sulfuric acid, and 4wt% sodium chloride;
  • a hydrophobic polypropylene salt-blocking and anti-corrosion layer is deposited on a metal foam block wrapped with a super-hydrophilic copper-nickel coating to obtain a gradient wetting metal foam block; wherein the helium gas flow rate is 180 sccm, the propylene gas flow rate is 60 sccm, the pressure is 500 mToor, the duty cycle is 80%, the power is 50 W, and the reaction time is 120 minutes;
  • step (3) immersing the gradient wetting copper foam block prepared in step (3) in water, taking it out after immersion for 20 minutes, and brushing off excess water; then immersing it in a mixed solution consisting of 0.1wt% ferroferric oxide nanoparticles (particle size of 100nm), 10wt% reduced graphene oxide (diameter of 5 ⁇ m, number of layers of 8 layers), 2wt% carbon nanotubes (diameter of 50nm), 2wt% iodine bismuth oxide particles (particle size of 2 ⁇ m), 2wt% PDMS, 0.03wt% curing agent and n-hexane, immersing it for 15 minutes, taking it out, and thermally curing it at 80°C. 120 minutes, a hydrophobic photothermal evaporation layer with micro-nano structure is generated.
  • a mixed solution consisting of 0.1wt% ferroferric oxide nanoparticles (particle size of 100nm), 10wt% reduced graphene oxide (
  • the water contact angle of the upper surface of the composite material prepared in this embodiment is 156°, and the water contact angle of the lower surface is 0°; under the condition of simulated sunlight, the water evaporation rate is 2.7 kg m -2 h -1 , and the photothermal conversion efficiency is 93%.
  • Example 3 The inventors of this case also took the gradient wetting copper-nickel multilayer composite material obtained in Example 3 as an example and characterized and tested it:
  • FIG 2 it is a SEM picture of the upper surface of the gradient wetting copper-nickel multilayer composite material.
  • the contact angle picture of water on the upper surface of the gradient wetting copper-nickel multilayer composite material can be seen in Figure 3, and the contact angle picture of the lower surface with water can be seen in Figure 4.
  • Control Example 1 This control example is basically the same as Example 3, except that no sulfur-containing nickel plating layer is constructed.
  • the comparative example prepared lacks the sulfur-containing nickel plating layer, and the porous copper plating layer has poor adhesion to the substrate, so a complete composite material cannot be obtained.
  • Comparative Example 2 This comparative example is basically the same as Example 3, except that: a super-hydrophilic porous copper plating layer is not constructed.
  • the test showed that the water contact angle of the composite material prepared in this comparative example was 155° on the upper surface and 105° on the lower surface; under the condition of simulated sunlight, the water evaporation rate was 0.3 kg m -2 h -1 and the photothermal conversion efficiency was 12%.
  • Control Example 3 This control example is basically the same as Example 3, except that no hydrophobic polyolefin salt barrier and anti-corrosion layer is constructed.
  • the test showed that the water contact angle of the upper surface of the composite material prepared in this comparative example was 113°, and the water contact angle of the lower surface was 0°; under the condition of simulated sunlight, the water evaporation rate was 0.4 kg m -2 h -1 , and the photothermal conversion efficiency was 17%.
  • Comparative Example 4 This comparative example is basically the same as Example 3, except that: a hydrophobic photothermal evaporation layer with a micro-nano structure is not constructed.
  • the test showed that the water contact angle of the upper surface of the composite material prepared in this comparative example was 121°, and the water contact angle of the lower surface was 0°; under the condition of simulated sunlight, the water evaporation rate was 0.2 kg m -2 h -1 , and the photothermal conversion efficiency was 8%.

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Abstract

本申请公开了一种梯度润湿铜镍多层复合材料及其制备方法与应用。所述梯度润湿铜镍多层复合材料包括在厚度方向上依次层叠设置的超亲水铜镍镀层包裹的金属泡沫块体、疏水聚烯烃阻盐防腐层和具有微纳米结构的疏水光热蒸发层。所述制备方法包括：在金属泡沫块体上电沉积多孔铜镀层，形成超亲水铜镍镀层包裹的金属泡沫块体，之后沉积疏水聚烯烃阻盐防腐层，最后生成具有微纳米结构的疏水光热蒸发层，制得梯度润湿铜镍多层复合材料。本申请提供的梯度润湿铜镍多层复合材料的各功能层优势互补、多功能耦合，得形成自下而上的梯度润湿性多层复合材料，可用于光热海水淡化、光热污水净化等领域。

Description

梯度润湿铜镍多层复合材料及其制备方法与应用
本申请基于并要求于2022年11月11日递交的申请号为202211415794.9、发明名称为“梯度润湿铜镍多层复合材料及其制备方法与应用”的中国专利申请的优先权。
技术领域
本申请涉及一种复合材料，尤其涉及一种梯度润湿铜镍多层复合材料及其制备方法与应用，属于功能性材料技术领域。
背景技术
金属泡沫是一种新型的三维多孔材料，具有孔隙率高、比表面积大、机械强度好等优点，作为吸附材料、过滤材料、散热材料等在污水处理、光热海水淡化等领域具有强大应用强力。光热海水淡化利用太阳能转化而来的热能从海水、污水中获取净水，是解决清洁水资源短缺的一种有前景的净水技术。在光热海水淡化领域，金属泡沫材料导热系数高，能够将太阳能快速的转化成热能，促使水分子的快速蒸发，提高海水淡化能力。但是，当亲水性金属泡沫直接用于光热海水淡化时，海水中无机盐随着水分子一起传输到光热蒸发层，待水分蒸发后，无机盐会沉积、板结才光热转化材料表面，降低光热转化速率。并且，金属泡沫在高盐环境使用时易发生腐蚀，降低光热转化材料的机械稳定性与使用寿命。
发明内容
本申请的主要目的在于提供一种梯度润湿铜镍多层复合材料，以克服现有技术中的不足。
本申请的另一目的还在于提供相对应的梯度润湿铜镍多层复合材料的制备方法。
本申请的另一目的还在于提供所述梯度润湿铜镍多层复合材料的应用。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了一种梯度润湿铜镍多层复合材料，它包括在厚度方向上依次层叠设置的超亲水铜镍镀层包裹的金属泡沫块体、疏水聚烯烃阻盐防腐层和具有微纳米结构的疏水光热蒸发层。
本申请实施例还提供了一种梯度润湿铜镍多层复合材料的制备方法，其包括：
(1)将镍盐、含硫有机物、络合剂和表面活性剂混合，得到含硫镍电镀液；
以金属泡沫块体为第一阳极，使所述第一阳极、第一阴极与含硫镍电镀液共同构建第一电化学工作体系；使所述第一电化学工作体系通电，进行第一电沉积反应，在金属泡沫块体上沉积形成含硫镍镀层，制得含硫镍镀层包裹的金属泡沫块体；
(2)以所述含硫镍镀层包裹的金属泡沫块体为第二阳极，使所述第二阳极、第二阴极与铜电镀液共同构建第二电化学工作体系；使所述第二电化学工作体系通电，进行第二电沉积反应，生成多孔铜镀层，再进行烧结，得到超亲水铜镍镀层包裹的金属泡沫块体；
(3)在所述超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，得到梯度润湿金属泡沫块体；
(4)将所述梯度润湿金属泡沫块体浸入水中，再浸入纳米材料、碘氧化铋微米颗粒、PDMS、固化剂与有机溶剂组成的混合溶液中浸泡，最后进行热固化，生成具有微纳米结构的疏水光热蒸发层，获得梯度润湿铜镍多层复合材料。
本申请实施例还提供了由前述方法制备的梯度润湿铜镍多层复合材料。
本申请实施例还提供了前述梯度润湿铜镍多层复合材料于光热海水淡化或光热污水净化等领域中的应用。
与现有技术相比，本申请的有益效果包括：
1)本申请提供的梯度润湿铜镍多层复合材料各功能层优势互补，形成自下而上的梯度润湿性多层复合材料，可用于光热海水淡化/光热污水净化领域；
2)本申请的超亲水铜镍镀层包裹的金属泡沫块体的孔隙率高、亲水性好，为光热蒸发层快速供给水分子；并且机械强度好、化学稳定性优异，使得复合材料寿命长；
3)本申请的疏水聚烯烃阻盐防腐层可以阻止过量水分传输至光热蒸发层，有效阻止光热蒸发层上水膜的形成及光热的损失，并且抑制盐分在光热蒸发层的堆积及减少盐对超亲水铜镍镀层包裹的金属泡沫块体的腐蚀；
4)本申请的疏水光热蒸发层含有微纳米结构的纳米材料，具有很强的光吸收能力及光热转换能力，各功能层优势互补、多功能耦合，得到具有梯度润湿特性的高性能复合材料。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根 据这些附图获得其他的附图。
图1是本申请一典型实施方案中梯度润湿铜镍多层复合材料的结构示意图；
图2是本申请实施例3制备的梯度润湿铜镍多层复合材料上表面的SEM图片；
图3是本申请实施例3制备的梯度润湿铜镍多层复合材料上表面与水的接触角图片；
图4是本申请实施例3制备的梯度润湿铜镍多层复合材料下表面与水的接触角图片。
具体实施方式
鉴于上述现有技术中存在的问题，经过长期的研究和大量的实验，本案发明人提出了该技术方案，如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
作为本申请技术方案的一个方面，其所涉及的系一种梯度润湿铜镍多层复合材料，请参阅图1所示，其包括在厚度方向上依次层叠设置的超亲水铜镍镀层包裹的金属泡沫块体1、疏水聚烯烃阻盐防腐层2和具有微纳米结构的疏水光热蒸发层3。
进一步地，所述梯度润湿铜镍多层复合材料自下而上包括3层，分别为超亲水铜镍镀层包裹的金属泡沫块体1，以及依次覆盖在所述超亲水铜镍镀层包裹的金属泡沫块体1上的疏水疏水聚烯烃阻盐防腐层2和具有微纳米结构的疏水光热蒸发层3。本申请中，超亲水铜镍镀层包裹的金属泡沫块体的孔隙率高、亲水性好，为光热蒸发层快速供给水分子；并且机械强度好、化学稳定性优异，使得复合材料寿命长；疏水聚烯烃阻盐防腐层阻止过量水分传输至光热蒸发层，有效阻止光热蒸发层上水膜的形成及光热的损失，并且抑制盐分在光热蒸发层的堆积；疏水光热蒸发层含有微纳米结构的纳米材料，具有很强的光吸收能力及光热转换能力。
作为本申请技术方案的另一个方面，其还涉及一种梯度润湿铜镍多层复合材料的制备方法，其主要是利用电化学技术将超亲水铜镍镀层包裹在金属泡沫骨架上，提高其抗海水腐蚀能力与海水传输速率；再构筑超薄疏水聚烯烃阻盐防腐层，解决盐析与板结问题；最后构筑含有微纳米结构的纳米材料的疏水光热蒸发层，提高光吸收能力及光热转换能力。
在一些实施方案中，所述梯度润湿铜镍多层复合材料的制备方法包括以下步骤：
(1)将镍盐、含硫有机物、络合剂和表面活性剂混合，得到含硫镍电镀液；
以金属泡沫块体为第一阳极，使所述第一阳极、第一阴极与含硫镍电镀液共同构建第一电化学工作体系；使所述第一电化学工作体系通电，进行第一电沉积反应，在金属泡沫块体上沉积形成含硫镍镀层，制得含硫镍镀层包裹的金属泡沫块体；
(2)以所述含硫镍镀层包裹的金属泡沫块体为第二阳极，使所述第二阳极、第二阴极与铜电镀液共同构建第二电化学工作体系；使所述第二电化学工作体系通电，进行第二电沉积反应，生成多孔铜镀层，再进行烧结，得到超亲水铜镍镀层包裹的金属泡沫块体；
(3)在所述超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，得到梯度润湿金属泡沫块体；
(4)将所述梯度润湿金属泡沫块体浸入水中，再浸入纳米材料、碘氧化铋微米颗粒、PDMS、固化剂与有机溶剂组成的混合溶液中浸泡，最后进行热固化，生成具有微纳米结构的疏水光热蒸发层，获得梯度润湿铜镍多层复合材料。
在一些实施方案中，步骤(1)中，所述含硫镍电镀液包括5～25wt％镍盐、1～5wt％含硫有机物、0.05～11wt％络合剂和0.01～3wt％表面活性剂。
在一些实施方案中，步骤(1)中，所述镍盐包括硫酸镍和氯化镍等中的任意一种或两种的组合，但不限于此。
进一步地，所述含硫有机物包括苯磺酸、乙撑硫脲和苯甲酰磺酰亚胺等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述络合剂包括硼酸和柠檬酸等中的任意一种或两种的组合，但不限于此。
进一步地，所述表面活性剂包括十二烷基硫酸钠、二十二烷基三甲基氯化铵和乙基己基硫酸钠等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述金属泡沫块体的材质包括镍和铜等中的至少一种。
在一些实施方案中，步骤(1)中，所述第一电沉积反应的工艺条件包括：电流密度为1～10A/dm2，第一电沉积反应的温度为30～60℃，时间为1～100h。
进一步地，所述第一阴极可以是镍片，但不限于此。
在一些实施方案中，步骤(2)中，所述铜电镀液包括10～30wt％铜盐、1～10wt％酸和0.5～10wt％无机盐。
进一步地，所述铜盐包括硫酸铜和氯化铜等中的任意一种或两种的组合，但不限于此。
进一步地，所述酸包括硫酸和盐酸等中的任意一种或两种的组合，但不限于此。
进一步地，所述无机盐包括氯化钠和氯化钾等中的任意一种或两种的组合，但不限于此。
在一些实施方案中，步骤(2)中，所述第二电沉积反应的工艺条件包括：电流密度为0.5～10A/dm2，第二电沉积反应的温度为30～60℃，时间为0.1～2h。
在一些实施方案中，步骤(2)中，所述烧结的温度为200～600℃，时间为0.5～24h。
进一步地，所述第二阴极可以是铜片，但不限于此。
在一些实施方案中，所述多孔铜镀层所含孔洞的孔径为0.01～100μm，孔隙率为10～90％。
在一些实施方案中，步骤(3)具体包括：
采用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为100～200sccm，烯烃气体的流速为10～100sccm，压强为10～1000mToor，占空比为10％～100％，功率为40～80W，反应时间为10～180min。
进一步地，所述烯烃气体可以包括乙烯、丙烯、氯乙烯等中的任意一种或两种以上的组合，但不限于此。
在一些实施方案中，步骤(4)具体包括：
将所述梯度润湿金属泡沫块体浸入水中，浸泡10～30min后取出；再浸入0.1～10wt％纳米材料、0.1～10wt％碘氧化铋微米颗粒、0.1～10wt％PDMS、0.01～2wt％固化剂与有机溶剂组成的混合溶液中，浸泡1～30min后取出，最后于50～120℃热固化10～300min，生成具有微纳米结构的疏水光热蒸发层。
在一些实施方案中，步骤(4)中，所述碘氧化铋微米颗粒的粒径为0.1～5μm。
进一步地，所述纳米材料中包括零维纳米粒子、二维还原氧化石墨烯和一维碳纳米管中的至少一种，组成微纳米结构，即多级结构。具体的，所述纳米材料包括粒径为10～100nm的四氧化三铁纳米粒子、直径为100nm～5μm和片层数为1～8层的还原氧化石墨烯、直径为2～50nm的碳纳米管等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述有机溶剂可以包括氯仿、正己烷和乙酸乙酯等中的任意一种或两种以上的组合，但不限于此。
其中，作为一更为具体的实施方案之一，所述梯度润湿铜镍多层复合材料的制备方法可以包括以下步骤：
(1)将经过预处理的金属泡沫块体和镍片浸入步骤含硫镍电镀液A中，形成以金属泡沫块体为阳极、以镍片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为1～10A/dm2的还原电流，30～60℃电沉积反应1～100小时，得到含硫镍镀层包裹的金属泡沫块体；所述的含硫镍电镀液A包括5～25wt％镍盐、1～5wt％含硫有机物、0.05～11wt％络合剂和0.01～3wt％表面活性剂；
(2)将步骤(1)制备的含硫镍镀层包裹的金属泡沫块体和铜片浸入铜电镀液B中，形 成以含硫镍镀层包裹的金属泡沫块体为阳极、以铜片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为0.5～10A/dm2还原电流，30～60℃电沉积反应0.1～2小时，生成多孔铜镀层；再经过200～600℃烧结，得到超亲水铜镍镀层包裹的金属泡沫块体；所述的铜电镀液B包括10～30wt％铜盐、1～10wt％酸、0.5～10wt％无机盐；
(3)利用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为100～200sccm，烯烃气体流速为10～100sccm，压强为10～1000mToor，占空比为10％～100％，功率为40～80W，反应时间为10～180分钟；
(4)将步骤(3)制备的梯度润湿金属泡沫块体浸入水中，浸泡10～30分钟后取出，拂去多余水份；再浸入0.1～10wt％纳米材料、0.1～10wt％碘氧化铋微米颗粒、0.1～10wt％PDMS、0.01～2wt％固化剂与有机溶剂组成的混合溶液中，浸泡1～30分钟后取出，50～120℃热固化10～300分钟，生成具有微纳米结构的疏水光热蒸发层；所述碘氧化铋微米颗粒的粒径为0.1～5μm；所述纳米材料包括粒径为10～100nm的四氧化三铁纳米粒子、直径为100nm～5μm和片层为1～8层的还原氧化石墨烯、直径为2～50nm的碳纳米管中的任意一种或两种以上的组合。
综上所述，本申请以金属泡沫块体为载体，通过电沉积技术在所述载体层上电镀超亲水铜镍镀层，再利用低温等离子体技术在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，最后通过溶液浸涂法制备具有微纳米结构的疏水光热蒸发层，各功能层优势互补，形成自下而上的具有梯度润湿性的三层复合材料，可用于光热海水淡化/光热污水净化领域。
作为本申请技术方案的另一个方面，其还涉及由前述方法制备的梯度润湿铜镍多层复合材料。
在一些实施方案中，所述梯度润湿铜镍多层复合材料包括在厚度方向上依次层叠设置的超亲水铜镍镀层包裹的金属泡沫块体、疏水聚烯烃阻盐防腐层和具有微纳米结构的疏水光热蒸发层。
进一步地，所述超亲水铜镍镀层的厚度为0.1～300μm，孔隙率为50～85％。
进一步地，所述疏水聚烯烃阻盐防腐层的厚度为0.05～50μm。
进一步地，所述具有微纳米结构的疏水光热蒸发层的厚度为0.1～800μm。
进一步地，所述梯度润湿铜镍多层复合材料的上表面与水的接触角为151～157°，下表面 与水的接触角为0°，在模拟太阳光光照条件下，水蒸发速率为2.5～2.9kg m-2h-1，光热转化效率为91～95％。
本申请实施例的另一个方面还提供了前述梯度润湿铜镍多层复合材料于光热海水淡化或光热污水净化等领域中的应用。
藉由前述技术方案，本申请提供的梯度润湿铜镍多层复合材料各功能层优势互补，形成自下而上的梯度润湿性多层复合材料，可用于光热海水淡化/光热污水净化领域。
以下结合若干较佳实施例及附图对本申请的技术方案作更为详细的解释说明。以下所述的具体实施例仅用于进一步说明和解释本申请，并非是对本申请的限制；从本申请公开的内容联想到或导出的所有变形，均认为是本申请的保护范围。
实施例1
(1)将经过预处理的镍泡沫块体和镍片浸入步骤含硫镍电镀液A中，形成以金属泡沫块体为阳极、以镍片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为1A/dm2的还原电流，30℃电沉积反应100小时，得到含硫镍镀层包裹的金属泡沫块体；所述的含硫镍电镀液A包括5wt％硫酸镍、1wt％苯磺酸、0.05wt％硼酸和0.01wt％十二烷基硫酸钠；
(2)将步骤(1)制备的含硫镍镀层包裹的金属泡沫块体和铜片浸入铜电镀液B中，形成以含硫镍镀层包裹的金属泡沫块体为阳极、以铜片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为10A/dm2还原电流，60℃电沉积反应0.1小时，生成多孔铜镀层；再经过200℃烧结24h，得到超亲水铜镍镀层包裹的金属泡沫块体；所述的铜电镀液B包括10wt％硫酸铜、1wt％硫酸、0.5wt％氯化钠；
(3)利用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚乙烯阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为100sccm，乙烯气体流速为10sccm，压强为10mToor，占空比为10％，功率为40W，反应时间为180分钟；
(4)将步骤(3)制备的梯度润湿镍泡沫块体浸入水中，浸泡10分钟后取出，拂去多余水份；再浸入0.1wt％四氧化三铁纳米粒子(粒径为10nm)、10wt％碘氧化铋微米颗粒(粒径为0.1μm)、0.1wt％PDMS、0.01wt％固化剂与氯仿组成的混合溶液中，浸泡30分钟后取出，50℃热固化10分钟，生成具有微纳米结构的疏水光热蒸发层。
经测试，本实施例制备的复合材料的上表面的水接触角为152°，下表面的水接触角为0°；在模拟太阳光光照条件下，水蒸发速率为2.5kg m-2h-1、光热转化效率为91％。
实施例2
(1)将经过预处理的铜泡沫块体和镍片浸入步骤含硫镍电镀液A中，形成以金属泡沫块体为阳极、以镍片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为10A/dm2的还原电流，60℃电沉积反应1小时，得到含硫镍镀层包裹的金属泡沫块体；所述的含硫镍电镀液A包括25wt％氯化镍、5wt％乙撑硫脲、11wt％柠檬酸和3wt％二十二烷基三甲基氯化铵；
(2)将步骤(1)制备的含硫镍镀层包裹的金属泡沫块体和铜片浸入铜电镀液B中，形成以含硫镍镀层包裹的金属泡沫块体为阳极、以铜片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为0.5A/dm2还原电流，30℃电沉积反应2小时，生成多孔铜镀层；再经过600℃烧结0.5h，得到超亲水铜镍镀层包裹的金属泡沫块体；所述的铜电镀液B包括30wt％氯化铜、10wt％盐酸、10wt％氯化钾；
(3)利用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚氯乙烯阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为200sccm，氯乙烯气体流速为100sccm，压强为1000mToor，占空比为100％，功率为80W，反应时间为10分钟；
(4)将步骤(3)制备的梯度润湿铜泡沫块体浸入水中，浸泡30分钟后取出，拂去多余水份；再浸入10wt％还原氧化石墨烯(直径为100nm，片层数为1层)、0.1wt％碘氧化铋微米颗粒(粒径为5μm)、10wt％PDMS、2wt％固化剂与乙酸乙酯组成的混合溶液中，浸泡1分钟后取出，120℃热固化300分钟，生成具有微纳米结构的疏水光热蒸发层。
经测试，本实施例制备的复合材料的上表面的水接触角为157°，下表面的水接触角为0°；在模拟太阳光光照条件下，水蒸发速率为2.8kg m-2h-1、光热转化效率为94％。
实施例3
(1)将经过预处理的铜泡沫块体和镍片浸入步骤含硫镍电镀液A中，形成以金属泡沫块体为阳极、以镍片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为2A/dm2的还原电流，50℃电沉积反应48小时，得到含硫镍镀层包裹的金属泡沫块体；所述的含硫镍电镀液A包括15wt％硫酸镍、2wt％苯甲酰磺酰亚胺、1wt％硼酸和1wt％乙基己基硫酸钠；
(2)将步骤(1)制备的含硫镍镀层包裹的金属泡沫块体和铜片浸入铜电镀液B中，形成以含硫镍镀层包裹的金属泡沫块体为阳极、以铜片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为3A/dm2还原电流，40℃电沉积反应0.5小时，生成多孔铜 镀层；再经过450℃烧结2h，得到超亲水铜镍镀层包裹的金属泡沫块体；所述的铜电镀液B包括15wt％硫酸铜、5wt％硫酸、4wt％氯化钠；
(3)利用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚丙烯阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为150sccm，丙烯气体流速为40sccm，压强为600mToor，占空比为60％，功率为60W，反应时间为90分钟；
(4)将步骤(3)制备的梯度润湿铜泡沫块体浸入水中，浸泡20分钟后取出，拂去多余水份；再浸入2wt％碳纳米管(直径为2nm)、2wt％碘氧化铋颗粒(粒径为2μm)、2wt％PDMS、0.03wt％固化剂与氯仿组成的混合溶液中，浸泡15分钟后取出，80℃热固化120分钟，生成具有微纳米结构的疏水光热蒸发层。
经测试，本实施例制备的复合材料的上表面的水接触角为151°，下表面的水接触角为0°；在模拟太阳光光照条件下，水蒸发速率为2.9kg m-2h-1、光热转化效率为95％。
实施例4
(1)将经过预处理的铜泡沫块体和镍片浸入步骤含硫镍电镀液A中，形成以金属泡沫块体为阳极、以镍片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为2A/dm2的还原电流，50℃电沉积反应48小时，得到含硫镍镀层包裹的金属泡沫块体；所述的含硫镍电镀液A包括10wt％硫酸镍、3wt％苯甲酰磺酰亚胺、5wt％硼酸和2wt％乙基己基硫酸钠；
(2)将步骤(1)制备的含硫镍镀层包裹的金属泡沫块体和铜片浸入铜电镀液B中，形成以含硫镍镀层包裹的金属泡沫块体为阳极、以铜片为阴极的电化学工作体系；接通电源，于阳极和阴极之间施加电流密度为3A/dm2还原电流，40℃电沉积反应0.5小时，生成多孔铜镀层；再经过350℃烧结12h，得到超亲水铜镍镀层包裹的金属泡沫块体；所述的铜电镀液B包括15wt％硫酸铜、5wt％硫酸、4wt％氯化钠；
(3)利用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚丙烯阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为180sccm，丙烯气体流速为60sccm，压强为500mToor，占空比为80％，功率为50W，反应时间为120分钟；
(4)将步骤(3)制备的梯度润湿铜泡沫块体浸入水中，浸泡20分钟后取出，拂去多余水份；再浸入0.1wt％四氧化三铁纳米粒子(粒径为100nm)、10wt％还原氧化石墨烯(直径为5μm，片层数为8层)、2wt％碳纳米管(直径为50nm)、2wt％碘氧化铋颗粒(粒径为2μm)、2wt％PDMS、0.03wt％固化剂与正己烷组成的混合溶液中，浸泡15分钟后取出，80℃热固化 120分钟，生成具有微纳米结构的疏水光热蒸发层。
经测试，本实施例制备的复合材料的上表面的水接触角为156°，下表面的水接触角为0°；在模拟太阳光光照条件下，水蒸发速率为2.7kg m-2h-1、光热转化效率为93％。
本案发明人还以实施例3所获梯度润湿铜镍多层复合材料为例，对其进行了表征与测试：
如图2所示，为该梯度润湿铜镍多层复合材料上表面的SEM图片。该梯度润湿铜镍多层复合材料上表面的水的接触角图片可参阅图3所示，其下表面与水的接触角图片可参阅图4所示。
对照例1：本对照例与实施例3基本相同，区别之处在于：不构筑含硫镍镀层。
本对照例制备的缺少含硫镍镀层，多孔铜镀层与基体附着力差，无法得到完整的复合材料。
对照例2：本对照例与实施例3基本相同，区别之处在于：不构筑超亲水多孔铜镀层。
经测试，本对照例制备的复合材料的上表面的水接触角为155°，下表面的水接触角为105°；在模拟太阳光光照条件下，水蒸发速率为0.3kg m-2h-1、光热转化效率为12％。
对照例3：本对照例与实施例3基本相同，区别之处在于：不构筑疏水聚烯烃阻盐防腐层。
经测试，本对照例制备的复合材料的上表面的水接触角为113°，下表面的水接触角为0°；在模拟太阳光光照条件下，水蒸发速率为0.4kg m-2h-1、光热转化效率为17％。
对照例4：本对照例与实施例3基本相同，区别之处在于：不构筑具有微纳米结构的疏水光热蒸发层。
经测试，本对照例制备的复合材料的上表面的水接触角为121°，下表面的水接触角为0°；在模拟太阳光光照条件下，水蒸发速率为0.2kg m-2h-1、光热转化效率为8％。
此外，本案发明人还参照实施例1-实施例4的方式，以本说明书中列出的其它原料和条件等进行了试验，并同样制得了超亲水镍铜镀层包裹的金属泡沫块体、疏水聚烯烃阻盐防腐层、具有微纳米结构的疏水光热蒸发层，最终得到梯度润湿铜镍多层复合材料。
应当理解，以上仅是本申请的具体应用范例，对本申请的保护范围不构成任何限制。凡采用等同变换或者等效替换而形成的技术方案，均落在本申请权利保护范围之内。

Claims (10)

  1. 一种梯度润湿铜镍多层复合材料的制备方法，其特征在于，包括：
    (1)将镍盐、含硫有机物、络合剂和表面活性剂混合，得到含硫镍电镀液；
    以金属泡沫块体为第一阴极，使所述第一阴极、第一阳极与含硫镍电镀液共同构建第一电化学工作体系；使所述第一电化学工作体系通电，进行第一电沉积反应，在金属泡沫块体上沉积形成含硫镍镀层，制得含硫镍镀层包裹的金属泡沫块体；
    (2)以所述含硫镍镀层包裹的金属泡沫块体为第二阴极，使所述第二阴极、第二阳极与铜电镀液共同构建第二电化学工作体系；使所述第二电化学工作体系通电，进行第二电沉积反应，生成多孔铜镀层，再进行烧结，得到超亲水铜镍镀层包裹的金属泡沫块体；
    (3)在所述超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，得到梯度润湿金属泡沫块体；
    (4)将所述梯度润湿金属泡沫块体浸入水中，再浸入纳米材料、碘氧化铋微米颗粒、PDMS、固化剂与有机溶剂组成的混合溶液中浸泡，最后进行热固化，生成具有微纳米结构的疏水光热蒸发层，获得梯度润湿铜镍多层复合材料。
  2. 根据权利要求1所述的制备方法，其特征在于：步骤(1)中，所述含硫镍电镀液包括5～25wt％镍盐、1～5wt％含硫有机物、0.05～11wt％络合剂和0.01～3wt％表面活性剂；
    和/或，所述镍盐包括硫酸镍和氯化镍中的任意一种或两种的组合；和/或，所述含硫有机物包括苯磺酸、乙撑硫脲和苯甲酰磺酰亚胺中的任意一种或两种以上的组合；和/或，所述络合剂包括硼酸和柠檬酸中的任意一种或两种的组合；和/或，所述表面活性剂包括十二烷基硫酸钠、二十二烷基三甲基氯化铵和乙基己基硫酸钠中的任意一种或两种以上的组合；
    和/或，所述金属泡沫块体的材质包括镍和铜中的至少一种。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述第一电沉积反应的工艺条件包括：电流密度为1～10A/dm2，第一电沉积反应的温度为30～60℃，时间为1～100h；
    和/或，所述第一阳极包括镍片。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述铜电镀液包括10～30wt％铜盐、1～10wt％酸和0.5～10wt％无机盐；
    和/或，所述的铜盐包括硫酸铜和氯化铜中的任意一种或两种的组合；和/或，所述酸包括硫酸和盐酸中的任意一种或两种的组合；和/或，所述无机盐包括氯化钠和氯化钾中的任意一种或两种的组合。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述第二电沉积反应的工艺条件包括：电流密度为0.5～10A/dm2，第二电沉积反应的温度为30～60℃，时间为0.1～2h；
    和/或，所述烧结的温度为200～600℃，时间为0.5～24h；
    和/或，所述第二阳极包括铜片；
    和/或，所述多孔铜镀层所含孔洞的孔径为0.01～100μm，孔隙率为10～90％。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤(3)包括：采用低温等离子体技术，在超亲水铜镍镀层包裹的金属泡沫块体上沉积疏水聚烯烃阻盐防腐层，得到梯度润湿金属泡沫块体；其中，氦气流速为100～200sccm，烯烃气体的流速为10～100sccm，压强为10～1000mToor，占空比为10％～100％，功率为40～80W，反应时间为10～180min；
    其中，所述烯烃气体包括乙烯、丙烯、氯乙烯中的任意一种或两种以上的组合。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤(4)包括：将所述梯度润湿金属泡沫块体浸入水中，浸泡10～30min后取出；再浸入0.1～10wt％纳米材料、0.1～10wt％碘氧化铋微米颗粒、0.1～10wt％PDMS、0.01～2wt％固化剂与有机溶剂组成的混合溶液中，浸泡1～30min后取出，最后于50～120℃热固化10～300min，生成具有微纳米结构的疏水光热蒸发层；
    和/或，所述碘氧化铋微米颗粒的粒径为0.1～5μm；
    和/或，所述纳米材料包括粒径为10～100nm的四氧化三铁纳米粒子、直径为100nm～5μm和片层数为1～8层的还原氧化石墨烯和直径为2～50nm的碳纳米管中的任意一种或两种以上的组合；
    和/或，所述有机溶剂包括氯仿、正己烷和乙酸乙酯中的任意一种或两种以上的组合。
  8. 由权利要求1-7中任一项所述制备方法制得的梯度润湿铜镍多层复合材料，其特征在于，所述梯度润湿铜镍多层复合材料包括在厚度方向上依次层叠设置的超亲水铜镍镀层包裹的金属泡沫块体、疏水聚烯烃阻盐防腐层和具有微纳米结构的疏水光热蒸发层。
  9. 根据权利要求8所述的梯度润湿铜镍多层复合材料，其特征在于：所述超亲水铜镍镀层的厚度为0.1～300μm，孔隙率为50～85％；和/或，所述疏水聚烯烃阻盐防腐层的厚度为0.05～50μm；和/或，所述具有微纳米结构的疏水光热蒸发层的厚度为0.1～800μm；
    和/或，所述梯度润湿铜镍多层复合材料的上表面与水的接触角为151～157°，下表面与水的接触角为0°，模拟太阳光光照条件下，水蒸发速率为2.5～2.9kg m-2h-1，光热转化效率为91～95％。
  10. 权利要求8或9所述的梯度润湿铜镍多层复合材料于光热海水淡化或光热污水净化领域中的应用。
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