CN114134536A - Sea urchin-shaped Ni @ Ni2P @ NiCoP electrode material and preparation method and application thereof - Google Patents

Sea urchin-shaped Ni @ Ni2P @ NiCoP electrode material and preparation method and application thereof Download PDF

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CN114134536A
CN114134536A CN202111447503.XA CN202111447503A CN114134536A CN 114134536 A CN114134536 A CN 114134536A CN 202111447503 A CN202111447503 A CN 202111447503A CN 114134536 A CN114134536 A CN 114134536A
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electrode material
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杨萍
晋聪聪
孙伟
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Anhui University of Science and Technology
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Abstract

The invention discloses sea urchin-shaped Ni @ Ni2A P @ NiCoP electrode material and a preparation method and application thereof relate to the technical field of preparation of transition metal phosphide electrode materials, and the preparation method comprises the following steps: placing foamed nickel in a container containing divalent nickel salt and K2S2O8In the aqueous solution, carrying out hydrothermal reaction, cooling, washing, drying and thermal annealing treatment to obtain a Ni @ NiO material; mixing divalent nickel salt, divalent cobalt salt and NH4Dissolving F and urea in deionized water, stirring, adding a mixed solution of DMF and DMSO, stirring, adding a Ni @ NiO material,hydrothermal reaction, washing and drying to obtain Ni @ NiO @ NiCo (OH)xA precursor; in a tube furnace, for Ni @ NiO @ NiCo (OH)xSubjecting the precursor to high-temperature phosphating treatment and cooling to obtain sea urchin-shaped Ni @ Ni2P @ NiCoP. The electrode material prepared by the invention can expose more active sites, has high HER catalytic activity, and can obtain catalytic efficiency which is comparable to that of commercial Pt/C.

Description

Sea urchin-shaped Ni @ Ni2P @ NiCoP electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of transition metal phosphide electrode materials, in particular to sea urchin-shaped Ni @ Ni2P @ NiCoP electrode material and a preparation method and application thereof.
Background
Seawater is one of the most abundant natural resources on earth. Seawater electrolysis is not only a promising method for generating clean hydrogen energy, but also has important significance for seawater desalination. The implementation of seawater electrolysis requires a powerful and effective electrocatalyst, and has been widely studied because transition metal phosphide has a very large specific surface area and thermodynamic stability, excellent electrical conductivity, and unique advantages in seawater total decomposition. Different from the defects of high energy consumption, low production efficiency and the like of the traditional hydrogen production process, the electrocatalytic decomposition hydrogen production process of seawater is simple, low in price and environment-friendly.
At present, the research on the transition metal phosphide mainly realizes the improvement of the catalytic activity of the material from the design and controllable synthesis of the material by regulating the appearance and the component structure of the material.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides sea urchin-shaped Ni @ Ni2The P @ NiCoP electrode material can expose more active sites and has high HER catalytic activity.
The invention provides sea urchin-shaped Ni @ Ni2The preparation method of the P @ NiCoP electrode material comprises the following steps:
s1, pretreatment of the foamed nickel: cutting the foamed nickel into a proper size, and cleaning;
s2, synthesis of Ni @ NiO: putting the cut foam nickel into the nickel salt containing divalent nickel and K2S2O8Heating the aqueous solution to perform hydrothermal reaction, cooling, washing, drying, and performing thermal annealing treatment in an air atmosphere to obtain a Ni @ NiO material;
S3、Ni@NiO@NiCo(OH)xsynthesis of a precursor: mixing divalent nickel salt, divalent cobalt salt and NH4Dissolving F and urea in deionized water, stirring and mixing, then adding a mixed solution of DMF and DMSO,stirring, adding Ni @ NiO material, heating to perform hydrothermal reaction, washing and drying to obtain Ni @ NiO @ NiCo (OH)xA precursor; wherein the volume ratio of DMF to DMSO is 2: 1;
S4、Ni@Ni2synthesis of P @ NiCoP: mixing Ni @ NiO @ NiCo (OH)xTransferring the precursor into a tubular furnace, placing hypophosphite at the upper air inlet of the air path of the tubular furnace, introducing inert gas for high-temperature phosphating, and cooling to obtain echinoid Ni @ Ni2P@NiCoP。
Preferably, the divalent nickel salt is one of nickel nitrate, nickel chloride and nickel acetate; the divalent cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt acetate.
Preferably, in S2, the divalent nickel salt and K are contained2S2O8In the aqueous solution of (2), Ni in the divalent nickel salt2+Has a molar concentration of 0.04-0.05mol/L, K2S2O8The molar concentration of (b) is 0.01-0.02 mol/L.
Preferably, in S2, heating to 145-155 ℃ and keeping for 9-11h for hydrothermal reaction; thermal annealing treatment is carried out for 1-3h at 380-420 ℃.
Preferably, in S3, after dissolving in deionized water, Ni is in divalent nickel salt2+And Co in divalent cobalt salts2+In a molar ratio of 1: 2, the total molar concentration of metal ions is 0.08-0.15mol/L, NH4The molar concentration of F is 0.08-0.15mol/L, and the molar concentration of urea is 0.25-0.30 mol/L.
Preferably, in S3, after the mixture of DMF and DMSO is added, the volume percentage of the mixture in the system is 8-12 vt%.
Preferably, in S3, the hydrothermal reaction is carried out by heating to 100-110 ℃ and keeping for 9-11 h.
Preferably, in S4, the high-temperature phosphating treatment is maintained at 340-360 ℃ for 1.5-2.5 h.
The invention also provides sea urchin-shaped Ni @ Ni prepared by the method2P @ NiCoP electrode material.
The invention also provides the sea urchin-shaped Ni @ Ni2The application of the P @ NiCoP electrode material in catalyzing alkaline electrolysis water hydrogen evolution reaction.
The invention also provides the sea urchin-shaped Ni @ Ni2The application of the P @ NiCoP electrode material in catalyzing the total hydrolysis of alkaline seawater.
Has the advantages that: the method grows NiO nano-sheets on a foamed nickel substrate through a hydrothermal method and heat treatment, and then grows the NiO nano-sheets in a three-solvent system (H)2In O/DMF/DMSO), depositing a NiCo (OH) x precursor on a NiO nano-sheet framework by a hydrothermal method to form a hierarchical heterogeneous nano-structure, and finally performing high-temperature phosphating treatment to successfully prepare the sea urchin-shaped Ni @ Ni2P @ NiCoP electrode material. The NiO nano-sheet synthesized in the first hydrothermal process is utilized to provide a growth site for the cluster-shaped nanoneedle growing in the second hydrothermal process, and the structure can fully contact with an electrolyte, expose an active site and enhance the HER performance of the catalyst. In addition, a nano-spherical structure similar to sea urchins is obtained by adding surface structure regulators DMF and DMSO in a hydrothermal process and regulating the ratio of the surface structure regulators DMF and DMSO, and the nano-spherical structure has more excellent catalytic activity compared with the nano-spherical structure obtained by adding only one MSO or DMF, and the changed shape benefits from a large active area, high surface activity and favorable ion and gas diffusion channels and has excellent HER activity. The electrode material prepared by the invention can obtain catalytic efficiency which is comparable to commercial Pt/C, and has high HER catalytic activity.
Drawings
FIG. 1 shows sea urchin-like Ni @ Ni of the present invention2A synthetic schematic diagram of a P @ NiCoP electrode material;
FIG. 2 shows sea urchin-like Ni @ Ni prepared in example 1 of the present invention2SEM picture of P @ NiCoP electrode material;
FIG. 3 is an XRD pattern of the material prepared in example 1 of the present invention; wherein a is Ni @ NiO, b is Ni @ NO @ NCO, c is Ni @ NP @ NCP (H), d is Ni @ NP @ NCP (F), e is Ni @ NP @ NCP (SO), and F is Ni @ NP @ NCP (F/SO);
FIG. 4 shows sea urchin-like Ni @ Ni prepared in example 1 of the present invention2XPS plot of P @ NiCoP electrode material;
FIG. 5 is a LSV plot of the material prepared in example 1 of the present invention;
FIG. 6 is a graph of the Tafel slope for the material prepared in example 1 of the present invention;
FIG. 7 is a graph of the LSV in seawater of the material prepared in example 1 of the present invention;
FIG. 8 is an EIS diagram of the material prepared in example 1 of the present invention;
FIG. 9 shows sea urchin-like Ni @ Ni prepared in example 1 of the present invention2LSV diagram of water full decomposition of P @ NiCoP electrode material in different electrolytes;
FIG. 10 shows sea urchin-like Ni @ Ni prepared in example 1 of the present invention2And (3) a time potential v-t curve of P @ NiCoP electrode material as a catalyst for the total decomposition of water.
Detailed Description
As shown in FIG. 1, it is sea urchin-shaped Ni @ Ni2The synthesis process of the P @ NiCoP nano-structure composite material is shown in a schematic diagram. Firstly, synthesizing a NiO nano sheet on a foam nickel substrate by adopting a hydrothermal method; then in a three-solvent system (H)2O/DMF/DMSO) by hydrothermal reaction of NiCo (OH)xDepositing the precursor on the NiO nano-sheet framework to form a hierarchical heterogeneous nano-structure; finally, carrying out high-temperature phosphating treatment on the heterostructure composite material in inert atmosphere to successfully prepare the echinoid Ni @ Ni2P @ NiCoP nanostructured catalyst.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Sea urchin-shaped Ni @ Ni2The preparation method of the P @ NiCoP electrode material comprises the following steps:
(1) pretreatment of foamed nickel: cutting foam nickel NF (3X 2.5 cm)2) Ultrasonic washing in acetone, hydrochloric acid, deionized water and ethanol respectively to remove impurities and oxide layers on the surface, washing with deionized water to neutrality, drying and standing for later use.
(2) Synthesis of Ni @ NiO: the cleaned nickel foam was transferred to a polystyrene (PPL) -lined stainless steel autoclave (50ml) containing homogeneous Ni (NO)3)2·6H2O (380mg) and K2S2O8(100mg) dissolved in 30ml of H2Solution in O. Thereafter, the autoclave was sealed and kept at 150 ℃ for 10 hours. After the reaction kettle is cooled to room temperature, taking out a sample and using for separationThe seed water and ethanol were washed several times and dried overnight at 60 ℃ under vacuum. And then carrying out thermal annealing on the base material in the air at 400 ℃ for 2h to obtain the Ni @ NiO material.
(3)Ni@NiO@NiCo(OH)xSynthesis of a precursor: generally, 1mM Ni (NO) is weighed3)2·6H2O、2mM Co(NO3)2·6H2O、3mM NH4F and 7.5mM urea were dissolved in 27mL deionized water and stirred at room temperature for 10 minutes. Then, a mixed solution of 2mL of DMF and 1mL of DMSO was added slowly, and stirring was continued for 10 minutes. After the solution was homogeneous, it was transferred to a 50mL Teflon lined steel autoclave with Ni @ NiO. After hydrothermal reaction at 100 ℃ for 11 hours, washed with deionized water to obtain Ni @ NiO @ NiCo (OH)xThe precursor was then dried in an oven at 60 ℃.
(4)Ni@Ni2Synthesis of P @ NiCoP: 0.75g NaH was placed upstream of the porcelain boat2PO2·H2O powder, downstream of which was placed Ni @ NiO @ NiCo (OH)xPrecursor sample at N2The tube furnace was heated to 350 ℃ under an atmosphere and held for 2 h. When the temperature is naturally cooled to room temperature, sea urchin-shaped Ni @ Ni is obtained2P @ NiCoP composite.
Example 2
Sea urchin-shaped Ni @ Ni2The preparation method of the P @ NiCoP electrode material comprises the following steps:
(1) pretreatment of foamed nickel: cutting foam nickel NF (3X 2.5 cm)2) Ultrasonic washing in acetone, hydrochloric acid, deionized water and ethanol respectively to remove impurities and oxide layers on the surface, washing with deionized water to neutrality, drying and standing for later use.
(2) Synthesis of Ni @ NiO: the cleaned nickel foam was transferred to a polystyrene (PPL) -lined stainless steel autoclave (50ml) containing homogeneous Ni (NO)3)2·6H2O (350mg) and K2S2O8(85mg) dissolved in 30ml of H2Solution in O. Thereafter, the autoclave was sealed and kept at 145 ℃ for 11 hours. After the reaction kettle is cooled to room temperature, the sample is taken out, washed with deionized water and ethanol for several times, and dried overnight at 60 ℃ in a vacuum atmosphere. However, the device is not suitable for use in a kitchenAnd then carrying out thermal annealing on the base material in the air at 380 ℃ for 3h to obtain the Ni @ NiO material.
(3)Ni@NiO@NiCo(OH)xSynthesis of a precursor: typically, 0.8mM Ni (NO) is weighed3)2·6H2O、1.6mM Co(NO3)2·6H2O、2.5mM NH4F and 7mM urea were dissolved in 27mL deionized water and stirred at room temperature for 10 minutes. Then, a mixed solution of 1.6mL of DMF and 0.8mL of DMSO was added slowly, and stirring was continued for 10 minutes. After the solution was homogeneous, it was transferred to a 50mL Teflon lined steel autoclave with Ni @ NiO. After hydrothermal reaction at 100 ℃ for 11 hours, washed with deionized water to obtain Ni @ NiO @ NiCo (OH)xThe precursor was then dried in an oven at 60 ℃.
(4)Ni@Ni2Synthesis of P @ NiCoP: 0.75g NaH was placed upstream of the porcelain boat2PO2·H2O powder, downstream of which was placed Ni @ NiO @ NiCo (OH)xPrecursor sample at N2The tube furnace was heated to 340 ℃ under an atmosphere and held for 2.5 h. When the temperature is naturally cooled to room temperature, sea urchin-shaped Ni @ Ni is obtained2P @ NiCoP composite.
Example 3
Sea urchin-shaped Ni @ Ni2The preparation method of the P @ NiCoP electrode material comprises the following steps:
(1) pretreatment of foamed nickel: cutting foam nickel NF (3X 2.5 cm)2) Ultrasonic washing in acetone, hydrochloric acid, deionized water and ethanol respectively to remove impurities and oxide layers on the surface, washing with deionized water to neutrality, drying and standing for later use.
(2) Synthesis of Ni @ NiO: the cleaned nickel foam was transferred to a polystyrene (PPL) -lined stainless steel autoclave (50ml) containing homogeneous Ni (NO)3)2·6H2O (420mg) and K2S2O8(150mg) was dissolved in 30ml of H2Solution in O. Thereafter, the autoclave was sealed and kept at 155 ℃ for 9 hours. After the reaction kettle is cooled to room temperature, the sample is taken out, washed with deionized water and ethanol for several times, and dried overnight at 60 ℃ in a vacuum atmosphere. Then carrying out thermal annealing on the base material in air at 420 ℃ for 1h to obtain Ni @NiO material.
(3)Ni@NiO@NiCo(OH)xSynthesis of a precursor: generally, 1.2mM Ni (NO) is weighed3)2·6H2O、2.4mM Co(NO3)2·6H2O、4mM NH4F and 8mM urea were dissolved in 27mL deionized water and stirred at room temperature for 10 minutes. Then, a mixed solution of 2.4mL of DMF and 1.2mL of DMSO was added slowly, and stirring was continued for 10 minutes. After the solution was homogeneous, it was transferred to a 50mL Teflon lined steel autoclave with Ni @ NiO. After hydrothermal reaction at 110 ℃ for 9 hours, washed with deionized water to obtain Ni @ NiO @ NiCo (OH)xThe precursor was then dried in an oven at 60 ℃.
(4)Ni@Ni2Synthesis of P @ NiCoP: 0.75g NaH was placed upstream of the porcelain boat2PO2·H2O powder, downstream of which was placed Ni @ NiO @ NiCo (OH)xPrecursor sample at N2The tube furnace was heated to 360 ℃ under an atmosphere and held for 2.5 h. When the temperature is naturally cooled to room temperature, sea urchin-shaped Ni @ Ni is obtained2P @ NiCoP composite.
Sea urchin-shaped Ni @ Ni prepared in the examples of the invention2And (3) carrying out characterization and performance test on the P @ NiCoP composite material.
The following materials, Ni @ NiO, Ni @ NO @ NCO, Ni @ NP @ NCP (H), Ni @ NP @ NCP (F), Ni @ NP @ NCP (SO), and Ni @ NP @ NCP (F/SO), were prepared as follows:
ni @ NiO: the sea urchin-shaped Ni @ Ni used in example 12The P @ NiCoP electrode material is prepared in the steps (1) and (2);
ni @ NO @ NCO: the sea urchin-shaped Ni @ Ni used in example 12The preparation method of the P @ NiCoP electrode material comprises the steps (1), (2) and (3), and then the obtained Ni @ NiO @ NiCo (OH)xPlacing the precursor in N2Heating to 350 ℃ in a tubular furnace under the atmosphere, keeping for 2 hours, and naturally cooling to room temperature to obtain the product;
ni @ NP @ NCP (H): ni @ Ni-Haichang-Medicumk-like in example 12The preparation of the P @ NiCoP electrode material is different only in that: in the step (3), 3mL of deionized water is replaced by 2mL of a mixed solution of DMF and 1mL of DMSO;
ni @ NP @ NCP (F): in example 1Sea urchin shaped Ni @ Ni2The preparation of the P @ NiCoP electrode material is different only in that: in the step (3), 3mL of DMF is replaced by a mixed solution of 2mL of DMF and 1mL of DMSO;
ni @ NP @ NCP (SO): ni @ Ni-Haichang-Medicumk-like in example 12The preparation of the P @ NiCoP electrode material is different only in that: in the step (3), 3mL of DMSO is replaced by 2mL of a mixed solution of DMF and 1mL of DMSO;
ni @ NP @ NCP (F/SO): ni @ Ni prepared for inventive example 12P @ NiCoP composite.
(a) characterization
SEM characterization:
FIG. 2 shows Ni @ Ni2SEM image of P @ NiCoP electrode material shows that the appearance of the composite material is greatly changed by adding DMF/DMSO, and Ni @ Ni2The structure of the P @ NiCoP is in a nanometer spherical shape similar to that of sea urchin, but the surface of the P @ NiCoP is still covered with uniform and compact cluster-shaped nanometer needles, so that the sea urchin-shaped structure can further increase the surface area of the composite material and promote the electrocatalytic performance of the composite material.
Characterization by XRD
The chemical composition of the composite material obtained was investigated by XRD. Typical XRD patterns are shown in FIG. 3, and diffraction peaks at 44.6 °, 52.0 ° and 76.6 ° can be found in all diffraction patterns, which can be attributed to NF, corresponding to the (111), (200), (220) crystal planes of Ni phase (JCPDF No. 70-0989). Peaks in curve a at 37.3 °, 43.4 ° and 63.0 ° may be assigned to the (111), (200) and (220) planes of NiO (JCPDF No. 73-1519). In curve b, in addition to the peaks of NiO, diffraction peaks at 31.1 °, 36.7 °, 59.1 ° and 65.0 ° were found, and the peaks were classified as NiCo2O4(JCPDF No.20-0781) species of (220), (311), (511) and (440) crystal planes. Thus, the sample corresponding to curve b can be identified as Ni @ NiO @ NiCo2O4. After the phosphating treatment, diffraction peaks with the same intensity and size can be observed in all the curves c, d, e and f, are positioned at 41.0 degrees, 47.6 degrees and 54.4 degrees and are similar to Ni2The (111), (210) and (300) planes of P (JCPDF No.74-1385) and NiCoP (JCPDF No.71-2336) are completely coincident. The peaks at 54.7 ° and 55.3 ° correspond to the (002), (211) crystals of NiCoPAnd (5) kneading. Therefore, DMSO and DMF are added to only change the microscopic morphology of the catalyst, no reaction occurs to generate new substances, and all phosphatized samples can be defined as Ni @ Ni2P@NiCoP。
XPS characterization
XPS measurements were further used to probe Ni @ Ni2Surface composition and oxidation state of P @ NiCoP. From the survey spectrum (FIG. 4a), it was found that Ni, Co, P, O, and C elements were present on the surface of the electrode. The C element (C1 s, 284.6eV) is mainly from environmental pollution and is used as a reference for calibrating the obtained XPS spectrum. Ni @ Ni2Ni2P of P @ NiCoP3/2The core energy level spectrum (FIG. 4b) shows three peaks with binding energies of 853.0, 856.8 and 861.9eV, respectively, which should be correlated with Ni-P, Ni-PO, respectivelyxAnd satellite peaks. Here, the binding energy of 853.0 is very close to that of metallic Ni (852.6eV), indicating the presence of a partially charged Ni species (Ni)δ+δ may be close to 0). Similarly, converted Ni @ Ni due to Co-P formation2Co 2P of P @ NiCoP3/2The fragment (FIG. 4c) has a new peak at 778.4eV and the binding energy was also found to be slightly higher than that of metallic Co (778.2eV), indicating that Co has a partial positive charge (Co-N-)δ+). The peak at 781.8eV is attributable to the Co oxidation state, which is associated with Co-POxAnd (4) correlating. While the peak at 786.1eV is related to the oscillating satellite peak (Sat.). Fig. 4d shows the P2P region where two double peaks are observed, with main peak binding energies of 129.9 and 134.5eV, respectively. The former can be classified as reduced phosphorus in the form of metal phosphide, with a binding energy of 129.9eV slightly lower than that of elemental P (130.0eV), indicating that the P moiety is negatively charged (P)δ-). Thus, P can act as a base to capture positively charged protons during electrocatalysis. The latter being classified as phosphate species (P)5+) Mainly from P on the surface2O5And PO4 3-Is performed. In fact, the O-P peak also gave the same results at 531.5eV in the O1s spectrum (FIG. 4 e). The additional peak at 532.8eV is associated with a large amount of adsorbed water at the surface.
(II) electrochemical Performance testing
1. HER activity in 1mol/L KOH electrolyte
We first performed three electrodes at room temperature (25 ℃ C.)The prepared electrode materials were evaluated for HER activity in 1mol/LKOH electrolyte in the polar system. The Linear Sweep Voltammogram (LSV) of Ni @ NiO, Ni @ NO @ NCO, Ni @ NP @ NCP (H), Ni @ NP @ NCP (F), Ni @ NP @ NCP (SO), Ni @ NP @ NCP (F/SO) nanostructures, and commercial Pt/C are shown in FIG. 5. Compared to Ni @ NiO (258.7, 352.2, and 380.5mV), Ni @ NO @ NCO (156.7, 261.2, and 303mV), Ni @ NP @ NCP (H) (93.2, 173.2, and 221.2mV), Ni @ NP @ NCP (SO) (107.2, 200.2, and 250.2mV), and Ni @ NP @ NCP (F) (74.2, 157.7, and 201.2mV), Ni @ NP @ NCP (F/SO) nanostructures provided 10, 100, and 300mA cm at low overpotentials of 68.2, 139.2, and 185.7mV, respectively-2Current density of (a), HER performance exceeds that of commercial Pt/C catalysts even at 193.2mV overpotential.
The Tafel slope of the prepared nanostructures was also calculated from the LSV curve to accurately explore their HER kinetics. As shown in FIG. 6, with Ni @ NiO (104.05mV dec)-1)、Ni@NO@NCO(92.95mV dec-1)，Ni@NP@NCP(H)(79.92mV dec-1)、Ni@NP@NCP(SO)(83.32mV dec-1)、Ni@NP@NCP(F)(79.4mV dec-1) In contrast, the Ni @ NP @ NCP (F/SO) nanostructure showed a smaller Tafel slope of 71.64mV dec-1Only slightly higher than commercial Pt/C, indicating that it has rapid HER reaction kinetics.
2. Alkaline simulation of HER Activity in seawater electrolyte (1M KOH +0.5M NaCl)
Then, we investigated HER activity in alkaline simulated seawater electrolyte (1M KOH +0.5M NaCl). As shown in FIG. 7, the Ni @ NP @ NCP (F/SO) nanostructured catalyst still exhibited excellent HER catalytic activity, requiring overpotentials of 80.2, 155.7, and 198.9mV to achieve 10, 100, and 300mAcm, respectively-2The current density of (1). This property is very close to that of the 1M KOH electrolyte, indicating that the NF @ NP @ NCP (F/SO) nanostructures still have good HER properties in alkaline-modified saline.
To gain a deeper understanding of HER reaction kinetics, EIS tests were also performed (fig. 8). Compared with Ni @ NiO (2.2 omega), Ni @ NO @ NCO (1.52 omega), Ni @ NP @ NCP (H) (0.93 omega), Ni @ NP @ NCP (SO) (1.24 omega), and Ni @ NP @ NCP (F) (0.44 omega), the Ni @ NP @ NCP (F/SO) nanostructure shows a minimum transfer resistance (Rct) of 0.3 omega, which proves that the nanostructure has the fastest electron transfer rate and the lowest electrical impedance, and contributes to excellent HER activity.
3. Test for Total hydrolysis Performance
Inspired by the excellent HER performance of the catalyst, the Ni @ NP @ NCP (F/SO) nanostructure was assembled as the cathode and anode in a two-electrode alkaline cell (without diaphragm or membrane) and the overall seawater decomposition performance was further investigated. Impressively, strong catalytic performance was achieved by the synthetic Ni @ NP @ NCP (F/SO) electrode. The electrolytic cell also exhibits excellent overall water-splitting activity in both alkaline solvents and alkaline simulated seawater electrolytes. As shown in FIG. 9, 100mA cm of NaCl was generated in 1M KOH and 1M KOH +0.5M NaCl at room temperature (25 ℃ C.)-2The cell voltage required for current density was as low as 1.697 and 1.724V, respectively. In particular, our cell can produce 300mA cm in 1M KOH +0.5M NaCl electrolyte at a voltage of 1.822V-2The high current density meets the requirement of realizing the high current density required by industry under low voltage.
Operational durability is also a very important indicator for evaluating the performance of an electrolytic cell. As shown in FIG. 10, the cell was in alkaline solvent and alkaline simulated seawater electrolyte at 200mA cm-2The high-voltage seawater desalination device can keep excellent integral seawater decomposition performance after running for 24 hours under the constant current density, and the working voltage is not obviously changed, thereby proving the great potential of the high-voltage seawater desalination device in the aspect of large-scale application.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. Sea urchin-shaped Ni @ Ni2The preparation method of the P @ NiCoP electrode material is characterized by comprising the following steps of:
s1, pretreatment of the foamed nickel: cutting the foamed nickel into a proper size, and cleaning;
s2, synthesis of Ni @ NiO: will be cut outThe foamed nickel is placed in a container containing divalent nickel salt and K2S2O8Heating the aqueous solution to perform hydrothermal reaction, cooling, washing, drying, and performing thermal annealing treatment in an air atmosphere to obtain a Ni @ NiO material;
S3、Ni@NiO@NiCo(OH)xsynthesis of a precursor: mixing divalent nickel salt, divalent cobalt salt and NH4Dissolving F and urea in deionized water, stirring and mixing, then adding a mixed solution of DMF and DMSO, stirring, adding a Ni @ NiO material, heating for hydrothermal reaction, washing and drying to obtain Ni @ NiO @ NiCo (OH)xA precursor; wherein the volume ratio of DMF to DMSO is 2: 1;
S4、Ni@Ni2synthesis of P @ NiCoP: mixing Ni @ NiO @ NiCo (OH)xTransferring the precursor into a tubular furnace, placing hypophosphite at the upper air inlet of the air path of the tubular furnace, introducing inert gas for high-temperature phosphating, and cooling to obtain echinoid Ni @ Ni2P@NiCoP。
2. Sea urchin-like Ni @ Ni as claimed in claim 12The preparation method of the P @ NiCoP electrode material is characterized in that the divalent nickel salt is one of nickel nitrate, nickel chloride and nickel acetate; the divalent cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt acetate.
3. Sea urchin-like Ni @ Ni as claimed in claim 12The preparation method of the P @ NiCoP electrode material is characterized in that S2 contains divalent nickel salt and K2S2O8In the aqueous solution of (2), Ni in the divalent nickel salt2+Has a molar concentration of 0.04-0.05mol/L, K2S2O8The molar concentration of (b) is 0.01-0.02 mol/L.
4. Sea urchin-like Ni @ Ni as claimed in claim 12The preparation method of the P @ NiCoP electrode material is characterized in that in S2, the P @ NiCoP electrode material is heated to 145-155 ℃ and kept for 9-11h for hydrothermal reaction; thermal annealing treatment is carried out for 1-3h at 380-420 ℃.
5. Sea urchin shape according to claim 1Ni@Ni2The preparation method of the P @ NiCoP electrode material is characterized in that Ni in divalent nickel salt is dissolved in deionized water in S32+And Co in divalent cobalt salts2+In a molar ratio of 1: 2, the total molar concentration of metal ions is 0.08-0.15mol/L, NH4The molar concentration of F is 0.08-0.15mol/L, and the molar concentration of urea is 0.25-0.30 mol/L; after the mixed solution of DMF and DMSO is added, the volume percentage of the mixed solution in the system is 8-12 vt%.
6. Sea urchin-like Ni @ Ni as claimed in claim 12The preparation method of the P @ NiCoP electrode material is characterized in that in S3, the hydrothermal reaction is carried out by heating to 100 ℃ and maintaining at 110 ℃ for 9-11 h.
7. Sea urchin-like Ni @ Ni as claimed in claim 12The preparation method of the P @ NiCoP electrode material is characterized in that in S4, high-temperature phosphating treatment is carried out for 1.5-2.5h at the temperature of 340-.
8. Sea urchin-like Ni @ Ni prepared by the method as claimed in any one of claims 1 to 72P @ NiCoP electrode material.
9. Sea urchin-like Ni @ Ni as claimed in claim 82The application of the P @ NiCoP electrode material in catalyzing alkaline electrolysis water hydrogen evolution reaction.
10. Sea urchin-like Ni @ Ni as claimed in claim 82The application of the P @ NiCoP electrode material in catalyzing the total hydrolysis of alkaline seawater.
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