CN110952112A - Graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and preparation method and application thereof - Google Patents
Graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrode materials, in particular to a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and a preparation method and application thereof. The invention provides a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material, which comprises the following steps of: providing foamed nickel @ graphene; placing the foamed nickel @ graphene in an acid solution for etching to obtain etched foamed nickel @ graphene; and carrying out phosphating treatment on the etched foam nickel @ graphene to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material. By adopting the preparation method provided by the invention, nickel phosphide can be wrapped in the interlayer of the graphene and the foamed nickel, active site exposure, mass transfer and electron transfer are improved, and the stability and the energy conversion efficiency of the composite material are further improved.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and a preparation method and application thereof.
Background
With the increase in the number of global populations and the continued development of socio-economic, energy demand has continued to increase accordingly. Energy shortage and environmental deterioration caused by the massive use of non-renewable energy have been one of the most important global problems facing the 21 st century in humans. The development of energy conversion and storage devices provides great opportunities for solving energy and environmental problems, and the energy conversion and storage devices are widely applied to the fields of hydrogen fuel automobiles, aerospace, electronic products, artificial intelligence and the like, the electrochemical performance of the energy conversion and storage devices is closely related to the structure and the property of an electrode material, and the design and the research and development of the electrode material with excellent structure can well improve the electrochemical performance (such as overpotential, conductivity, specific capacitance and the like), so that the utilization rate, the storage efficiency and the production efficiency of electric energy are greatly improved, and further considerable economic benefits are generated.
The traditional electrode material mainly comprises a pure carbon-based material (such as mesoporous carbon, carbon nano tubes and the like) and transition metal oxide or hydroxide, wherein the pure carbon-based material has few active sites and low discharge capacity; the poor conductivity and poor cycling stability of transition metal oxides or hydroxides inhibit their use in energy storage and conversion. At present, the composite material of graphene, transition metal oxide and hydroxide is widely researched, different types and abundant active sites can be provided by combining interfaces among different phases, and the interface electron transmission can be regulated and controlled by different phases, so that the continuous and rapid occurrence of multi-step reactions becomes possible.
Recent research shows that the transition metal phosphide shows metalloid properties due to the interaction between metal and phosphorus element 3d orbitals, and is more suitable for being used as an electrode material for energy conversion and storage compared with other electrode materials. However, the graphene and transition metal phosphide are mainly obtained from powder materials in the current report, expensive conductive polymers are consumed when the graphene and transition metal phosphide are prepared into an electrode, the preparation process is complicated, the powder falls off due to gas generated in the hydrogen production process, and the stability is poor. In addition, for powder materials, due to the flexibility of graphene, the graphene and the transition metal phosphide are stacked together, and the spatial positions of the graphene and the transition metal phosphide are difficult to regulate, so that the exposure of active sites and the transmission of substances in the reaction process are influenced.
Chinese patent CN104810165B discloses a method for preparing a nickel phosphide/graphene composite film material, which takes a metal nickel substrate as a carrier, immerses the metal nickel substrate into dispersion liquid of red phosphorus and graphene oxide, and synthesizes the nickel phosphide/graphene composite film material through hydrothermal reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material, which comprises the following steps of:
(1) providing foamed nickel @ graphene, wherein the graphene in the foamed nickel @ graphene is a shell layer, and the foamed nickel is a core layer;
(2) placing the foamed nickel @ graphene in an acid solution for etching to obtain etched foamed nickel @ graphene; the concentration of hydrogen ions in the acidic solution is 0.05-10 mol/L;
(3) and carrying out phosphating treatment on the etched foam nickel @ graphene to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
Preferably, the acidic solution in step (2) is an acid solution, or a mixed solution of an acid and a salt;
the acid solution comprises one or more of a nitric acid solution, a sulfuric acid solution, a perchloric acid solution, a hydrochloric acid solution and a hydrofluoric acid solution; the concentration of the acid solution is 0.05-5 mol/L;
the acid in the mixed solution of the acid and the salt comprises one or more of nitric acid, sulfuric acid, perchloric acid, hydrochloric acid and hydrofluoric acid; the salt in the mixed solution of the acid and the salt comprises one or more of copper salt, iron salt and silver nitrate; the concentration of the acid in the mixed solution of the acid and the salt is 0.05-5 mol/L, and the concentration of the salt is 0.05-5 mol/L.
Preferably, the etching temperature is 5-60 ℃.
Preferably, the etching manner comprises stirring, ultrasonic treatment or standing;
when the etching mode is stirring, the stirring speed is 500-2000 r/min, and the time is 10-120 min;
when the etching mode is ultrasonic, the power of the ultrasonic is 50-300W, and the time is 5-120 min;
and when the etching mode is standing, the standing time is 5 min-24 h.
Preferably, the phosphating treatment comprises hydrothermal phosphating or gas-phase reduction phosphating;
the hydrothermal phosphorization comprises the following steps: placing the etched foamed nickel @ graphene in a phosphorus-containing hydrochloric acid water dispersion liquid, and carrying out a first hydrothermal reaction to obtain a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material;
the gas-phase reduction phosphorization comprises the following steps: placing the etched foam nickel @ graphene in a hydrochloric acid aqueous solution, and carrying out a second hydrothermal reaction to obtain a complex; and placing the composite and sodium hypophosphite in the same furnace body, and calcining to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
Preferably, the source of phosphorus in the phosphorus-containing aqueous hydrochloric acid dispersion comprises red phosphorus and/or sodium hypophosphite;
when the phosphorus in the phosphoric hydrochloric acid water dispersion liquid is red phosphorus, the mass of the red phosphorus is 0.05-0.20 g;
when the phosphorus in the phosphoric hydrochloric acid water dispersion liquid is sodium hypophosphite, the mass of the sodium hypophosphite is 0.1-0.3 g.
Preferably, the temperature of the first hydrothermal reaction is 220-300 ℃ and the time is 10-36 h.
Preferably, the temperature of the second hydrothermal reaction is 100-200 ℃ and the time is 8-24 h;
the calcining temperature is 200-400 ℃, and the time is 0.5-3 h.
The invention provides a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material which is prepared by the preparation method in the technical scheme, wherein the thickness of the nickel phosphide interlayer is 50-200 nm.
The invention also provides application of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material in energy conversion.
The invention provides a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material, which comprises the following steps of: (1) providing foamed nickel @ graphene; taking graphene as a shell layer and foam nickel as a core layer; (2) placing the foamed nickel @ graphene in an acid solution for etching to obtain etched foamed nickel @ graphene; the concentration of hydrogen ions in the acidic solution is 0.05-10 mol/L; (3) and carrying out phosphating treatment on the etched foam nickel @ graphene to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material. According to the method, foam nickel and graphene wrapped on the surface of foam nickel are used as precursors, and gaps are formed at the interface of the graphene and the foam nickel after the foam nickel and the graphene are etched by an acid solution; through phosphating treatment, nickel ions are dissolved out of the surface of the foamed nickel, phosphorus elements are combined with the dissolved nickel ions through gaps to generate nickel phosphide, and then the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material is obtained. By adopting the preparation method provided by the invention, nickel phosphide can be wrapped in the interlayer of the graphene and the foamed nickel, active site exposure, mass transfer and electron transfer are improved, and the stability and the energy conversion efficiency of the composite material are further improved.
Drawings
Fig. 1 is a schematic diagram of a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material provided by the invention;
fig. 2 is an XRD chart, a raman spectrogram and a scanning electron microscope image of the nickel foam @ graphene prepared in the example of the present invention;
FIG. 3 is a 45000 times scanning electron microscope image of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material prepared in example 1 of the present invention;
FIG. 4 is a 600-fold scanning electron micrograph, a Raman spectrogram and an elemental analysis of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material prepared in example 2 of the present invention;
fig. 6 is a graph comparing the alkaline electrocatalytic hydrogen evolution performance of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material prepared in example 1 of the present invention and the nickel phosphide @ nickel structural material prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material, which comprises the following steps of:
(1) providing foamed nickel @ graphene, wherein the graphene in the foamed nickel @ graphene is a shell layer, and the foamed nickel is a core layer;
(2) placing the foamed nickel @ graphene in an acid solution for etching to obtain etched foamed nickel @ graphene; the concentration of hydrogen ions in the acidic solution is 0.05-10 mol/L;
(3) and carrying out phosphating treatment on the etched foam nickel @ graphene to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
The invention provides a preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material, which is shown in figure 1.
The invention provides foamed nickel @ graphene, which takes graphene as a shell layer and foamed nickel as a core layer. The source of the nickel foam @ graphene is not particularly limited in the invention, and the nickel foam @ graphene is prepared by a method well known to a person skilled in the artCan be prepared. In the embodiment of the present invention, the preparation method of the nickel foam @ graphene is preferably prepared by a chemical vapor deposition method with reference to a method (NatureMaterials,2011,10, 424-428) reported by kyemmingmuies, and the specific preparation method is as follows: in a horizontal tube furnace, heating foam nickel to 1050 ℃, introducing argon at the flow rate of 450sccm, introducing hydrogen at the flow rate of 50sccm, and removing oxides on the surface of the foam nickel to prepare for the growth of graphene on the surface of the foam nickel; and then introducing methane at the flow rate of 5sccm, stopping the reaction after 10min, and cooling to room temperature to obtain the foamed nickel @ graphene. The foam nickel and graphene prepared by the method are smooth in surface, and the graphene is uniformly wrapped on the surface of the foam nickel. In the invention, the number of the wrapped layers of the graphene is preferably one or more; the shape of the foamed nickel is preferably cylindrical, and the height multiplied by the surface area of the foamed nickel @ graphene is preferably 1mm multiplied by 2cm2、 1mm×1.5cm2Or 1 mm. times.3 cm2。
After the foam nickel @ graphene is obtained, the foam nickel @ graphene is placed in an acid solution to be etched, and the etched foam nickel @ graphene is obtained.
In the invention, the concentration of hydrogen ions in the acidic solution is preferably 0.05-10 mol/L, and more preferably 0.1-0.2 mol/L; the acidic solution is preferably: acid solutions, or mixed solutions of acids and salts. In the present invention, the acid solution preferably includes one or more of a nitric acid solution, a sulfuric acid solution, a perchloric acid solution, a hydrochloric acid solution, and a hydrofluoric acid solution; the concentration of the acid solution is preferably 0.05-5 mol/L, and more preferably 0.2-0.2 mol/L. In the present invention, the acid in the mixed solution of the acid and the salt preferably includes one or more of nitric acid, sulfuric acid, perchloric acid, hydrochloric acid, and hydrofluoric acid; the salt in the mixed solution of the acid and the salt preferably comprises one or more of copper salt, iron salt and silver nitrate; the concentration of the acid in the mixed solution of the acid and the salt is preferably 0.05-5 mol/L, and more preferably 0.2-2 mol/L; the concentration of the salt is preferably 0.05 to 5mol/L, more preferably 0.2 to 2 mol/L.
In the invention, when the size of the foamed nickel @ graphene is 1mm multiplied by (1.5-3) cm2When the acid solution is dissolvedThe volume of the solution is preferably 10-50 mL. According to the method, space is generated between the graphene and the foam nickel interface by utilizing acid etching, and the space is used for growth of a nickel phosphide nanosheet structure; according to the invention, the etching strength of the nickel foam @ graphene is controlled by regulating the concentration of hydrogen ions in the acidic solution, and the space between the graphene and nickel phosphide and the surface of nickel can be well regulated, so that more active site exposure is provided, faster material transmission is realized, and the efficiency of energy storage and conversion devices is greatly improved.
In the invention, the etching temperature is preferably 5-60 ℃, more preferably 25-40 ℃, and more preferably 30 ℃. In the present invention, the etching means preferably includes stirring, ultrasonication or standing;
when the etching mode is stirring, the stirring speed is preferably 500-2000 r/min, and more preferably 1000 r/min; the time is preferably 10-120 min, and more preferably 60-100 min;
when the etching mode is ultrasonic, the power of the ultrasonic is preferably 50-300W, and more preferably 200W; the time is preferably 5-120 min, and more preferably 15-30 min;
when the etching mode is standing, the standing time is preferably 5min to 24 hours, more preferably 0.5 to 20 hours, and further preferably 6 to 10 hours.
When the acid solution is used for etching the foamed nickel @ graphene, the acid reacts with nickel on the surface of the foamed nickel (nickel in contact with the graphene in the foamed nickel) to generate hydrogen and corresponding soluble nickel salt, and the nickel on the surface of the foamed nickel is etched; when the mixed solution of the acid solution and the salt solution is used for etching the foamed nickel @ graphene, the salt solution and nickel on the surface of the foamed nickel are subjected to a displacement reaction to obtain soluble nickel salt, and the surface of the foamed nickel is etched by combining with acid, so that the etching degree of the nickel on the surface of the foamed nickel can be better regulated and controlled.
After the etching is finished, preferably cleaning the solid substance obtained by etching; the cleaning step preferably comprises ethanol ultrasonic cleaning and deionized water ultrasonic cleaning which are sequentially carried out; the time for ultrasonic washing by the ethanol is preferably 1-10 min, and more preferably 5-8 min; the time for ultrasonic washing with deionized water is preferably 1-10 min, and more preferably 5-8 min.
After the etched foam nickel @ graphene is obtained, the etched foam nickel @ graphene is subjected to phosphating treatment to obtain a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material. In the present invention, the phosphating treatment preferably includes hydrothermal phosphating or vapor-phase reduction phosphating.
In the present invention, the hydrothermal phosphating preferably comprises the steps of: and placing the etched foam nickel @ graphene in a phosphorus-containing hydrochloric acid water dispersion liquid, and carrying out a first hydrothermal reaction to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material. In the present invention, the source of phosphorus in the phosphorus-containing aqueous hydrochloric acid dispersion preferably comprises red phosphorus and/or sodium hypophosphite; when the phosphorus in the phosphoric hydrochloric acid water dispersion liquid containing phosphorus is red phosphorus, the mass of the red phosphorus is preferably 0.05-0.20 g, and more preferably 0.05-0.1 g; when the phosphorus in the phosphoric hydrochloric acid water dispersion liquid containing phosphorus is sodium hypophosphite, the mass of the sodium hypophosphite is preferably 0.1-0.3 g, and more preferably 0.1-0.2 g; the concentration of hydrochloric acid in the phosphoric hydrochloric acid water dispersion liquid is preferably 0.002-0.02 mol/L, and more preferably 0.005-0.01 mol/L. The dosage ratio of the etched nickel foam @ graphene to the phosphorus-containing hydrochloric acid water dispersion liquid is not specially limited, and the etched nickel foam @ graphene is preferably completely immersed.
In the invention, the temperature of the first hydrothermal reaction is preferably 220-300 ℃, and more preferably 250-280 ℃; the time is preferably 10 to 36 hours, and more preferably 12 to 24 hours. Under the acidic condition, the nickel on the surface of the foam nickel is dissolved out to form Ni (H)2O)n 2+Ni (H) as hydrogen ions are consumed2O)n 2+Can be hydrolyzed to generate a nickel hydroxide nanosheet structure, and can generate nickel phosphide between foamed nickel and graphene in the presence of phosphorus at a proper temperature and reaction time.
In the present invention, the gas-phase reductive phosphating process preferably comprises the steps of: placing the etched foam nickel @ graphene in a hydrochloric acid aqueous solution, and carrying out a second hydrothermal reaction to obtain a complex; and placing the composite and sodium hypophosphite in the same furnace body, and calcining to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
In the invention, the concentration of the hydrochloric acid aqueous solution is preferably 0.002-0.02 mol/L, and more preferably 0.005-0.01 mol/L. The invention has no special limitation on the dosage ratio of the etched nickel foam @ graphene to the hydrochloric acid aqueous solution, and is suitable for completely immersing the etched nickel foam @ graphene. In the invention, the temperature of the second hydrothermal reaction is preferably 100-200 ℃, and more preferably 150 ℃; the time is preferably 8-24 h, and more preferably 10 h.
After the second hydrothermal reaction is completed, preferably drying the obtained solid substance to obtain a complex, wherein the drying temperature is preferably 30-100 ℃, and more preferably 50 ℃; the time is preferably 5 to 24 hours, and more preferably 12 hours.
After the composite is obtained, the composite and sodium hypophosphite are preferably placed in the same furnace body and calcined to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite. In the invention, the mass ratio of the complex to the sodium hypophosphite is preferably 1 (8-20), more preferably 1: 10; the complex and the sodium hypophosphite are preferably positioned in the furnace body in a relationship that the complex is downstream of the gas flow and the sodium hypophosphite is upstream of the gas flow. In the invention, the calcining temperature is preferably 200-400 ℃, and more preferably 300 ℃; the time is preferably 0.5-3 h, and more preferably 40 min. The invention converts nickel hydroxide in the interlayer into nickel phosphide through a calcination process.
The invention provides a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material which is prepared by the preparation method in the technical scheme, wherein the thickness of the nickel phosphide interlayer sheet structure is 50-200 nm, preferably 100nm, and the height of the nickel phosphide interlayer sheet structure is preferably 100-300 nm, preferably 200 nm. The graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material provided by the invention is rough in surface, and the graphene outer layer is preferably single-layer graphene or several layers of graphene; the inner layer of the nickel is preferably a cylindrical foam nickel frame, and the diameter of the cylindrical inner layer of the nickel is preferably 30-50 mu m.
The example results show that the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material provided by the invention contains nickel element, phosphorus element and carbon element, and the content of the nickel element is preferably 94.415%, the content of the phosphorus element is 5.065% and the content of the carbon element is 0.520% in terms of mass content.
The invention also provides an application of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material in energy conversion in the technical scheme, preferably, the composite electrocatalyst provided by the invention is used as a working electrode and used for hydrogen production by electrocatalytic cracking of water under an alkaline condition, and particularly, the temperature for hydrogen production by electrocatalytic cracking of water is preferably room temperature; the alkaline condition is preferably 1mol/L potassium hydroxide aqueous solution; the Shanghai Chenghua electrochemical workstation of model CHI760e was used, and a standard three-electrode system was used, with a saturated calomel electrode as the reference electrode and a carbon rod as the counter electrode. In the composite material provided by the invention, capacitance spaces can be provided between the graphene and the nickel phosphide and between the nickel phosphide and the nickel, and particularly in the electrocatalytic hydrogen evolution process, the dissociation of water is facilitated, so that the overpotential of the electrocatalytic water hydrogen evolution is reduced, and the energy utilization rate is improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of foamed nickel @ graphene: with reference to the method reported by Congress Ministry (Nature Materials,2011,10,424-428), the preparation was carried out by chemical vapor deposition: in a horizontal tube furnace, heating foam nickel to 1050 ℃, introducing argon at the flow rate of 450sccm, introducing hydrogen at the flow rate of 50sccm, and removing oxides on the surface of the foam nickel to prepare for the growth of graphene on the surface of the foam nickel; then introducing methane at the flow rate of 5sccm, stopping the reaction after 10min, and cooling to room temperature to obtain foamed nickel @ graphene;
the X-ray diffraction pattern of said nickel foam @ graphene is shown in fig. 2 (a), from which fig. 2 (a) it can be seen that only elemental nickel is present (XRD standard card No. 01-1258); the raman spectrum of the obtained nickel foam @ graphene is shown in (b) in fig. 2, and it can be confirmed from (b) in fig. 2 that graphene grows on the surface of the nickel foam; the scanning electron microscope image of the obtained nickel foam @ graphene is shown in (c) in fig. 2, and it can be seen from (c) in fig. 2 that the surface of the nickel foam @ graphene is smooth, which indicates that the graphene is uniformly wrapped on the surface of the nickel foam; through the analysis, the foam nickel @ graphene framework structure is successfully prepared and confirmed;
(2) the preparation method comprises the following steps of preparing a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material:
the size of the sample is 1mm multiplied by 2cm2The foamed nickel @ graphene is placed in 0.2mol/L hydrochloric acid aqueous solution, and is subjected to ultrasonic treatment for 15min at the temperature of 25 ℃, wherein the ultrasonic power is 200W; then sequentially ultrasonically cleaning the obtained solid substance for 8min by using ethanol and deionized water respectively to obtain etched foamed nickel @ graphene;
placing the obtained etched foamed nickel @ graphene in hydrochloric acid water dispersion liquid of red phosphorus, wherein the mass of the red phosphorus is 0.05g, and the concentration of hydrochloric acid is preferably 0.01 mol/L; carrying out hydrothermal reaction for 12h at 230 ℃ to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
The 45000-fold scanning electron microscope image of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material is shown in fig. 3; as shown in fig. 4 (a), a 600-fold scanning electron microscope image shows that, as can be seen from fig. 3 and 4 (a), the obtained composite material completely retains the three-dimensional framework structure of the original nickel foam, and the surface of the composite material is rough; a graphene thin layer with a thin surface like a cicada wing can be obviously seen from fig. 3, and a nickel phosphide nanosheet structure is wrapped under the graphene layer, so that a space is generated between the graphene and a foam nickel interface due to acid etching, and the growth of the nickel phosphide nanosheet structure is realized; the Raman spectrum of the obtained composite material is shown in FIG. 4 (b), and it can be seen from FIG. 4 (b) that 1349cm is shown in the Raman spectrum-1And 1604 cm-1Description of the peaks appearingThe existence of graphene in the product indicates the structure of the graphene coated by the outer layer; an element analysis diagram of the obtained composite material is shown in (c) in fig. 4, and it can be seen from (c) in fig. 4 that the composite material prepared by the invention contains nickel element, phosphorus element and carbon element, and the mass percentages of the nickel element, the phosphorus element and the carbon element are respectively as follows: 94.415 wt.%, 5.065 wt.%, and 0.520 wt.%, the successful preparation of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite can be fully demonstrated by the results of fig. 4.
Example 2
Preparing foamed nickel @ graphene by adopting the same preparation method as that of the embodiment 1;
the size of the sample is 1mm multiplied by 1.5cm2The foamed nickel @ graphene is placed in a mixed aqueous solution of 2mol/L copper chloride and 1mol/L hydrochloric acid, and is stirred for 60min at the temperature of 40 ℃ at the speed of 2000 r/min; then sequentially ultrasonically cleaning the obtained solid substance for 5min by using ethanol and deionized water respectively to obtain etched nickel foam @ graphene;
placing the etched foamed nickel @ graphene in a hydrochloric acid water dispersion liquid of sodium hypophosphite, wherein the mass of the sodium hypophosphite in the hydrochloric acid water dispersion liquid of the sodium hypophosphite is 0.2g, and the concentration of hydrochloric acid is 0.01 mol/L; carrying out hydrothermal reaction for 24h at 280 ℃ to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
The scanning electron microscope image of the obtained composite material is shown in fig. 5, and as can be seen from fig. 5, the composite material with the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework is successfully prepared.
Example 3
Preparing foamed nickel @ graphene by adopting the same preparation method as that of the embodiment 1;
the size of the sample is 1mm multiplied by 3cm2The foamed nickel @ graphene is placed in 2mol/L hydrochloric acid aqueous solution, and is stirred for 120min at the temperature of 30 ℃ and the speed of 1000 r/min; then sequentially ultrasonically cleaning the obtained solid substances for 10min by using ethanol and deionized water respectively to obtain etched nickel foam @ graphene;
placing the etched foamed nickel @ graphene in 0.01mol/L hydrochloric acid aqueous solution, performing hydrothermal treatment for 10h at 150 ℃, then drying for 10h at 50 ℃, placing the dried composite in a tubular furnace, and performing phosphating treatment for 40min at 300 ℃ by using sodium hypophosphite as a phosphorus source to obtain a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material; the structure and composition of the obtained composite material are similar to those of the embodiments 1-2.
Comparative example 1
Placing foamed nickel into 0.01mol/L hydrochloric acid aqueous solution, carrying out hydrothermal treatment for 10h at 150 ℃, drying, placing in a tubular furnace, and carrying out phosphating treatment for 40min at 300 ℃ by using sodium hypophosphite as a phosphorus source to obtain the nickel phosphide @ nickel structural material.
And (3) performance testing:
the alkaline electrocatalytic hydrogen evolution performance of the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material prepared in the example 1 and the nickel phosphide @ nickel structure material prepared in the comparative example 1 is tested, and the specific method comprises the following steps: the model of Shanghai Chenghua electrochemical workstation is CHI760e, a standard three-electrode system is adopted, the composite material provided by the invention is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and an electrolyte solution is a 1mol/L potassium hydroxide aqueous solution;
the test results are shown in fig. 6, wherein a in fig. 6 is the nickel phosphide @ nickel structural material prepared in comparative example 1; in fig. 6, b is the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material prepared in example 1; as can be seen from FIG. 6, the composite material prepared in example 1 was at 50mA cm-2The overpotential of the material is about 100mV lower than that of the material of the comparative example 1, and the performance is obviously improved; the composite material provided by the invention has more excellent energy conversion efficiency.
In the composite material provided by the invention, due to the conductivity of the graphene, capacitance layers constructed between the graphene and the nickel phosphide and between the nickel phosphide and the nickel foam are beneficial to the occurrence of the dissociation process of water, and the composite material provided by the invention is in a range of 10 mA-cm-2Overpotential of up to about 50mV, which can approach platinum carbon (Pt 20 wt.%, about 35mV is widely reported for platinum-impregnated carbon); the composite material provided by the inventionThe material is heated for a long time (72h) and at a high current density (20mA cm)-2) The electrochemical hydrogen evolution performance is not obviously attenuated; comprehensively shows that the composite material prepared by the invention has good electrochemical hydrogen evolution performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material comprises the following steps:
(1) providing foamed nickel @ graphene, wherein the graphene in the foamed nickel @ graphene is a shell layer, and the foamed nickel is a core layer;
(2) placing the foamed nickel @ graphene in an acid solution for etching to obtain etched foamed nickel @ graphene; the concentration of hydrogen ions in the acidic solution is 0.05-10 mol/L;
(3) and carrying out phosphating treatment on the etched foam nickel @ graphene to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
2. The method according to claim 1, wherein the acidic solution in the step (2) is an acid solution, or a mixed solution of an acid and a salt;
the acid solution comprises one or more of a nitric acid solution, a sulfuric acid solution, a perchloric acid solution, a hydrochloric acid solution and a hydrofluoric acid solution; the concentration of the acid solution is 0.05-5 mol/L;
the acid in the mixed solution of the acid and the salt comprises one or more of nitric acid, sulfuric acid, perchloric acid, hydrochloric acid and hydrofluoric acid; the salt in the mixed solution of the acid and the salt comprises one or more of copper salt, iron salt and silver nitrate; the concentration of the acid in the mixed solution of the acid and the salt is 0.05-5 mol/L, and the concentration of the salt is 0.05-5 mol/L.
3. The method according to claim 1, wherein the etching temperature is 5-60 ℃.
4. A producing method according to claim 1 or 3, characterized in that the etching manner includes stirring, ultrasonic or standing;
when the etching mode is stirring, the stirring speed is 500-2000 r/min, and the time is 10-120 min;
when the etching mode is ultrasonic, the power of the ultrasonic is 50-300W, and the time is 5-120 min;
and when the etching mode is standing, the standing time is 5 min-24 h.
5. The production method according to claim 1, wherein the phosphating treatment includes hydrothermal phosphating or vapor-phase reduction phosphating;
the hydrothermal phosphorization comprises the following steps: placing the etched foamed nickel @ graphene in a phosphorus-containing hydrochloric acid water dispersion liquid, and carrying out a first hydrothermal reaction to obtain a graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material;
the gas-phase reduction phosphorization comprises the following steps: placing the etched foam nickel @ graphene in a hydrochloric acid aqueous solution, and carrying out a second hydrothermal reaction to obtain a complex; and placing the composite and sodium hypophosphite in the same furnace body, and calcining to obtain the graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material.
6. A method according to claim 5, characterized in that the source of phosphorus in the aqueous dispersion of hydrochloric acid containing phosphorus comprises red phosphorus and/or sodium hypophosphite;
when the phosphorus in the phosphoric hydrochloric acid water dispersion liquid is red phosphorus, the mass of the red phosphorus is 0.05-0.20 g;
when the phosphorus in the phosphoric hydrochloric acid water dispersion liquid is sodium hypophosphite, the mass of the sodium hypophosphite is 0.1-0.3 g.
7. The preparation method according to claim 5 or 6, wherein the temperature of the first hydrothermal reaction is 220-300 ℃ and the time is 10-36 h.
8. The preparation method according to claim 5, wherein the temperature of the second hydrothermal reaction is 100-200 ℃ and the time is 8-24 h;
the calcining temperature is 200-400 ℃, and the time is 0.5-3 h.
9. The graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material is prepared by the preparation method of any one of claims 1 to 8, and the thickness of the nickel phosphide interlayer is 50-200 nm.
10. The use of the graphene outer layer @ nickel phosphide interlayer @ nickel inner frame composite material of claim 9 in energy conversion.
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