A nickel-based compound-amorphous chromium family heterojunction self-supporting electrode and a preparation method and application thereof

Abstract

The application discloses a kind of nickel-based compound-amorphous chromium family heterojunction self-supporting electrode and its preparation method and application, by covering on carbon cloth fiber nickel-based compound nanocrystal-amorphous chromium family heterojunction thin layer composition self-supporting electrode, amorphous chromium family component is chromium or molybdenum or tungsten, first using electrodeposition method in carbon cloth fiber surface covers a layer of amorphous nickel-chromium or nickel-molybdenum or nickel-tungsten thin layer, then heat treatment under different atmosphere, make amorphous nickel into different nickel-based compound nanocrystal, while high melting point chromium family still exists in amorphous form, to obtain different nickel-based compound-amorphous chromium family heterostructure, applied to electrocatalytic hydrogen evolution reaction;Because the nickel-chromium family metal obtained by electrodeposition is amorphous, annealing treatment in different atmosphere, it is in-situ conversion from bottom to top, so the nickel-based compound nanocrystal formed is very small in size, increases catalytic active site, improves HER catalytic efficiency and durability in electrolyte.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of electrocatalytic materials, and particularly relates to a nickel-based compound-amorphous chromium family heterojunction self-supporting electrode and a preparation method and application thereof. BACKGROUND

[0002] Hydrogen, as a high-calorific value, clean and pollution-free zero-carbon energy, plays an important role in energy transformation. The method of producing hydrogen by electrolysis of water has the advantages of safety, environmental protection, controllable scale, high product purity, etc. However, the hydrogen evolution reaction (HER) of water electrolysis is limited by slow reaction kinetics, and requires high-performance catalytic electrodes. Although noble metal platinum-based materials have high HER electrocatalytic activity, their stability is low and the cost is high, making it difficult to achieve large-scale application. Nickel-based materials are widely used due to their multiple chemical states, excellent electron donation and acceptance ability, and low price. However, single-phase nickel-based compounds as electrocatalysts have problems such as insufficient active site number and lack of controllability, so by introducing other components, a heterostructure is constructed to increase the active site density and regulate the electronic structure.

[0003] The method disclosed in the document with Chinese patent application number 202210504090.2 and title "A foam nickel with heterojunction nanosheet layers grown on the surface and a preparation method and application thereof" grows NiO and Ni3S2 crystalline-crystalline heterojunction nanosheets on the surface of the foam nickel and is applied to lithium-sulfur batteries. The document with Chinese patent application number 202410798698.X and title "A nickel compound-phosphide sub-nanometer hybrid self-supporting electrode, a preparation method and application thereof" discloses a nickel compound-phosphide sub-nanometer hybrid self-supporting electrode with hydrogen evolution and oxygen evolution dual-function catalytic performance. By heat treatment in different atmospheres, in-situ crystallization and conversion of the amorphous thin layer are achieved, obtaining different nickel compound-phosphide sub-nanometer hybrid structures. By using a simple chemical plating-heat treatment method, an amorphous nickel-phosphorus thin layer is covered on the surface of carbon cloth fibers, and then in-situ crystallization and conversion are achieved in different anion source atmospheres, thereby obtaining a series of nickel compound and phosphide sub-nanometer hybrid hetero-thin layers. However, the nickel-based compound-based heterostructure disclosed in the above two patent documents is a crystalline-crystalline heterojunction composed of different compound grains. The fixed crystal structure of the crystalline material limits the hybridization and synergy between the hetero-components, and therefore the catalytic active site density is still low and the catalytic efficiency is not high. SUMMARY

[0004] The present application aims to solve the problem of limited hybridization and synergy of the existing crystalline-crystalline heterojunction nickel-based compound-based heterostructure, and provides a nickel-based compound-amorphous chromium family heterojunction self-supporting electrode and a preparation method thereof. The prepared self-supporting electrode in amorphous form can improve the catalytic efficiency and durability in electrolyte. The present application also provides the application of the self-supporting electrode.

[0005] In order to achieve the above object, the technical scheme of the nickel-based compound-amorphous chromium family heterojunction self-supporting electrode provided by the application is as follows: composed of a nickel-based compound nanocrystal-amorphous chromium family heterojunction thin layer covering the carbon cloth fiber, wherein the nickel-based compound component is nickel disulfide, nickel sulfide, nickel diselenide, phosphide nickel, or nickel oxide, and the amorphous chromium family component is chromium, molybdenum or tungsten.

[0006] The technical scheme of the preparation method of the nickel-based compound-amorphous chromium family heterojunction self-supporting electrode provided by the application is as follows:

[0007] (1) first introduce active groups on the surface of the carbon cloth fiber, then clean with deionized water until the cleaning liquid is neutral, and then dry;

[0008] (2) using nickel-chromium plating solution or nickel-molybdenum plating solution or nickel-tungsten plating solution as electrolyte, a layer of nickel-chromium or nickel-molybdenum or nickel-tungsten thin layer with amorphous characteristics is covered on the surface of the dried carbon cloth fiber by electrodeposition to obtain amorphous nickel-chromium family metal / carbon cloth;

[0009] (3) placing the amorphous nickel-chromium family metal / carbon cloth in the downstream of a quartz boat, placing sublimed sulfur or selenium powder or sodium hypophosphite in the upstream of the quartz boat, then placing the quartz boat in a tube furnace, heating and keeping warm in nitrogen or argon, converting the amorphous nickel on the surface of the carbon cloth into nickel disulfide or nickel sulfide or nickel diselenide or phosphide nickel nanocrystal, and the chromium or molybdenum or tungsten still exists in amorphous form;

[0010] Or: placing the amorphous nickel-chromium family metal / carbon cloth in the quartz boat, placing the quartz boat in the tube furnace, heating and keeping warm in ammonia or air, converting the amorphous nickel on the surface of the carbon cloth into nickel nitride or nickel oxide nanocrystal, and the chromium or molybdenum or tungsten still exists in amorphous form.

[0011] Preferably, the formula of the nickel-chromium plating solution in step (2) is: 1g of NiSO4·6H2O, 1g of NiCl2·6H2O, 9.6g of CrCl3·6H2O, 7.7g of C6H8O7, 10.7g of Na3C6H5O7, 6.2g of H3BO3, 0.02g of CH3(CH2) 11OSO3Na and 100 mL deionized water; the formula of the nickel-molybdenum plating solution is: 3g Na2MoO4·2H2O, 6g NiSO4·6H2O, 2mL NH3·H2O, 8g Na3C6H5O7·2H2O, 2g NiCl·6H2O and 100 mL deionized water; the formula of the nickel-tungsten plating solution is 2.6g NiSO4·6H2O, 0.48g NiCl2·6H2O, 6.6-19.8g Na2WO4·2H2O, 12.9g Na3C6H5O7, 3.1g H3BO3 and 100 mL deionized water.

[0012] The application of the nickel-based compound-amorphous chromium family heterojunction self-supporting electrode provided by the application is applied to an electrocatalyst for hydrogen evolution reaction.

[0013] Compared with the prior art, the application has the following advantages and beneficial effects:

[0014] 1. Compared with the existing crystalline material, the amorphous state in the nickel-based compound-amorphous chromium family heterojunction self-supporting electrode has the advantages of easy reconfiguration and adjustable modification. One component of the heterojunction is amorphous, which can be hybridized with different crystal faces of the crystalline component without being limited by the crystal lattice mismatch, and the hybridization mode is more flexible. In addition, the amorphous component is usually dense and corrosion-resistant, so that the material has higher electrocatalytic stability.

[0015] 2. The application provides a simple and efficient electrodeposition-annealing conversion method to obtain a series of nickel-based compound-amorphous chromium family heterojunction self-supporting electrodes (including nickel disulfide-amorphous chromium / carbon cloth, nickel disulfide-amorphous molybdenum / carbon cloth, nickel sulfide-amorphous tungsten, nickel diselenide-amorphous chromium / carbon cloth, nickel diselenide-amorphous molybdenum / carbon cloth, nickel diselenide-amorphous tungsten / carbon cloth, diphosphide nickel-amorphous chromium / carbon cloth, diphosphide nickel-amorphous molybdenum / carbon cloth, diphosphide nickel-amorphous tungsten / carbon cloth, trinitride nickel-amorphous chromium / carbon cloth, trinitride nickel-amorphous molybdenum / carbon cloth, trinitride nickel-amorphous tungsten / carbon cloth, nickel oxide-amorphous chromium / carbon cloth, nickel oxide-amorphous molybdenum / carbon cloth, and nickel oxide-amorphous tungsten / carbon cloth). Since the nickel-chromium family metal obtained by electrodeposition is in an amorphous form, annealing treatment in different atmospheres causes in-situ conversion from bottom to top, so that the nickel-based compound nanocrystals formed are very small in size.

[0016] 3. The application fully utilizes the difference between nickel and chromium family metals in terms of crystallization conversion temperature, and a crystalline-amorphous heterojunction can be obtained from an amorphous plating layer by simple annealing treatment at a suitable temperature. Compared with the traditional method for preparing a crystalline-amorphous heterojunction, the method is simpler, more efficient and more universal.

[0017] 4. Compared with traditional nickel-based heteromaterials, the material prepared by this invention has a significantly increased number of catalytic active sites, improved HER catalytic efficiency and durability in electrolyte, and is suitable for industrial production. Attached Figure Description

[0018] Figure 1 The image shows a SEM image of Ni-Mo / CC-700 from Example 1.

[0019] Figure 2 The images shown are TEM images and selected area electron diffraction patterns of the Ni-Mo / CC-700 surface thin layer in Example 1, where a is the TEM image and b is the selected area electron diffraction pattern.

[0020] Figure 3 The XRD pattern of Ni-Mo / CC-700 in Example 1;

[0021] Figure 4 The 1 mol L of Ni-Mo / CC-700 saturated with N2 in Example 1 -1 HER polarization curves in KOH electrolyte;

[0022] Figure 5 The image shows a SEM image of Ni3N-a-Mo / CC-700 in Example 1.

[0023] Figure 6 This is a high-magnification TEM image of the Ni3N-a-Mo / CC-700 surface thin layer in Example 1;

[0024] Figure 7 The selected area electron diffraction pattern of the Ni3N-a-Mo / CC-700 surface thin layer in Example 1;

[0025] Figure 8 The XRD pattern of Ni3N-a-Mo / CC-700 in Example 1;

[0026] Figure 9 The above are XPS spectra of Ni3N-a-Mo / CC-700 in Example 1, where Figure a is the full XPS spectrum of Ni3N-a-Mo / CC-700, Figure b is the high-resolution spectrum of Ni 2p, Figure c is the high-resolution spectrum of Mo 3d, and Figure d is the high-resolution spectrum of N1s.

[0027] Figure 10 The 1 mol L of Ni3N-a-Mo / CC-700 saturated with N2 in Example 1 -1 HER polarization curves in KOH electrolyte;

[0028] Figure 11Current vs. time curve for Ni3N-a-Mo / CC-700 tested at -0.07 V vs. RHE constant potential in Example 1;

[0029] Figure 12 SEM image of Ni-Mo / CC-300 in Example 2;

[0030] Figure 13 HER polarization plot for Ni-Mo / CC-300 in N2-saturated 1 mol L -1 KOH electrolyte in Example 2;

[0031] Figure 14 SEM image of Ni-Mo / CC-1100 in Example 3;

[0032] Figure 15 HER polarization plot for Ni-Mo / CC-1100 in N2-saturated 1 mol L -1 KOH electrolyte in Example 3;

[0033] Figure 16 SEM image of NiS x -a-Mo / CC in Example 4;

[0034] Figure 17 XRD pattern of NiS x -a-Mo / CC in Example 4;

[0035] Figure 18 HER polarization plot for NiS x -a-Mo / CC in N2-saturated 1 mol L -1 KOH electrolyte in Example 4;

[0036] Figure 19 SEM image of NiSe2-a-Mo / CC in Example 5;

[0037] Figure 20 XRD pattern of NiSe2-a-Mo / CC in Example 5;

[0038] Figure 21 HER polarization plot for NiSe2-a-Mo / CC in N2-saturated 1 mol L -1 KOH electrolyte in Example 5;

[0039] Figure 22 SEM image of Ni2P-a-Mo / CC in Example 6;

[0040] Figure 23XRD pattern of Ni2P-a-Mo / CC in Example 6;

[0041] Figure 24 HER polarization curve plot of Ni2P-a-Mo / CC in Example 6 in 1 mol L -1 KOH electrolyte saturated with N2;

[0042] Figure 25 SEM image of NiO-a-Mo / CC in Example 7;

[0043] Figure 26 XRD pattern of NiO-a-Mo / CC in Example 7;

[0044] Figure 27 HER polarization curve plot of NiO-a-Mo / CC in Example 7 in 1 mol L -1 KOH electrolyte saturated with N2;

[0045] Figure 28 SEM image of Ni-W / CC-0.4 in Example 8, where Fig. a is a low magnification SEM image and Fig. b is a high magnification SEM image;

[0046] Figure 29 TEM image and selected area electron diffraction pattern of the surface thin layer of Ni-W / CC-0.4 in Example 8, where Fig. a is a TEM image and Fig. b is a selected area electron diffraction pattern;

[0047] Figure 30 XRD pattern of Ni-W / CC-0.4 in Example 8;

[0048] Figure 31 HER polarization curve plot of Ni-W / CC-0.4 in Example 8 in 1 mol L -1 KOH electrolyte saturated with N2;

[0049] Figure 32 SEM image of Ni3N-a-W / CC-0.4 in Example 8, where Fig. a is a low magnification SEM image and Fig. b is a high magnification SEM image;

[0050] Figure 33 TEM image and selected area electron diffraction pattern of the surface thin layer of Ni3N-a-W / CC-0.4 in Example 8, where Fig. a is a TEM image and Fig. b is a selected area electron diffraction pattern;

[0051] Figure 34 XRD pattern of Ni3N-a-W / CC-0.4 in Example 8;

[0052] Figure 35The following are XPS spectra of Ni3N-aW / CC-0.4 in Example 8: Figure a is the full XPS spectrum of Ni3N-aW / CC-0.4, Figure b is the high-resolution spectrum of Ni 2p, Figure c is the high-resolution spectrum of W 4f, and Figure d is the high-resolution spectrum of N1s.

[0053] Figure 36 In Example 8, Ni3N-aW / CC-0.4 was used in 1 mol L of N2-saturated solution. -1 HER polarization curves in KOH electrolyte;

[0054] Figure 37 The curve showing the change of current over time in Ni3N-aW / CC-0.4 during testing at a constant potential of -0.07V vs. RHE in Example 8;

[0055] Figure 38 In Example 9, Ni-W / CC-0.2 was saturated with N2 in a 1 mol L solution. -1 HER polarization curves in KOH electrolyte;

[0056] Figure 39 For example 10, Ni-W / CC-0.6 saturated with N2 is 1 mol L. -1 HER polarization curves in KOH electrolyte;

[0057] Figure 40 NiS in Example 11 x -aW / CC SEM images;

[0058] Figure 41 NiS in Example 11 x XRD pattern of -aW / CC;

[0059] Figure 42 NiS in Example 11 x -aW / CC in 1 mol L of N2 saturated -1 HER polarization curves in KOH electrolyte;

[0060] Figure 43 The image shown is a SEM image of NiSe2-aW / CC in Example 12.

[0061] Figure 44 The XRD pattern of NiSe2-aW / CC in Example 12;

[0062] Figure 45 The 1 mol L of NiSe2-aW / CC saturated with N2 in Example 12 -1 HER polarization curves in KOH electrolyte;

[0063] Figure 46 SEM image of Ni2P-a-W / CC in Example 13;

[0064] Figure 47 XRD pattern of Ni2P-a-W / CC in Example 13;

[0065] Figure 48 HER polarization curve of Ni2P-a-W / CC in Example 13 in 1 mol L -1 KOH electrolyte saturated with N2;

[0066] Figure 49 SEM image of NiO-a-W / CC in Example 14;

[0067] Figure 50 XRD pattern of NiO-a-W / CC in Example 14;

[0068] Figure 51 HER polarization curve of NiO-a-W / CC in Example 14 in 1 mol L -1 KOH electrolyte saturated with N2;

[0069] Figure 52 SEM image of Ni-Cr / CC in Example 15;

[0070] Figure 53 XRD pattern of Ni3N-a-Cr / CC in Example 15;

[0071] Figure 54 HER polarization curve of Ni3N-a-Cr / CC in Example 15 in 1 mol L -1 KOH electrolyte saturated with N2. DETAILED DESCRIPTION

[0072] The present application provides a nickel-based compound-amorphous chromium family heterojunction self-supporting electrode composed of a nickel-based compound nanocrystal-amorphous chromium family heterojunction thin layer covering the carbon cloth fiber, and the thickness of the thin layer is 0.2-1 microns; wherein the nickel-based compound component is nickel disulfide or nickel sulfide or nickel diselenide or phosphide di-nickel or nitrogen tri-nickel or nickel oxide, and the nanocrystal size is 5-10 nanometers; and the amorphous chromium family component is chromium or molybdenum or tungsten.

[0073] The method for preparing the above-mentioned nickel-based compound-amorphous chromium family heterojunction self-supporting electrode is to first cover an amorphous nickel-chromium or nickel-molybdenum or nickel-tungsten thin layer on the surface of the carbon cloth fiber by using an electrodeposition method; and then heat treatment is carried out under different atmospheres, so that the amorphous nickel is converted into different nickel-based compound nanocrystals, while the chromium family elements still exist in the form of amorphous, thereby obtaining different nickel-based compound-amorphous chromium family heterostructures, and the specific process is as follows:

[0074] (1) Preparation of amorphous nickel-chromium group thin layer on carbon cloth fiber

[0075] The carbon cloth is soaked in a 10% to 15% mass fraction nitric acid or sulfuric acid or mixed solution of sulfuric acid and nitric acid to introduce active groups on the fiber surface and improve hydrophilicity; then it is washed with deionized water until the washing liquid is neutral, and dried for standby use; an amorphous nickel-chromium or nickel-molybdenum or nickel-tungsten thin layer is covered on the surface of the carbon cloth fiber by using an electrodeposition method with a nickel-chromium plating solution or a nickel-molybdenum plating solution or a nickel-tungsten plating solution as an electrolyte, to obtain an amorphous nickel-chromium group metal / carbon cloth.

[0076] (2) Preparation of nickel-based compound-amorphous chromium group heterojunction thin layer on carbon cloth fiber

[0077] The amorphous nickel-chromium group metal / carbon cloth obtained in step (1) is placed downstream of a quartz boat, and sublimed sulfur or selenium powder or sodium hypophosphite is placed upstream; the mass ratio of the sublimed sulfur or selenium powder or sodium hypophosphite to the area of the amorphous nickel-chromium group metal / carbon cloth is 0.05 to 0.1 g cm -2 ; the quartz boat is placed in a tube furnace, and heated to 450 to 500°C in nitrogen or argon, and kept for 1 to 3 h, so that the amorphous nickel on the surface of the carbon cloth is converted into nickel disulfide or nickel sulfide or nickel diselenide or phosphide nanocrystals, while the difficult-to-crystallize chromium or molybdenum or tungsten still exists in an amorphous form.

[0078] Alternatively: the amorphous nickel-chromium group metal / carbon cloth obtained in step (1) is placed in a quartz boat; the quartz boat is placed in a tube furnace, and heated to 450 to 500°C in ammonia or air, and kept for 1 to 3 h, so that the amorphous nickel on the surface of the carbon cloth is converted into nickel nitride or nickel oxide nanocrystals, while the difficult-to-crystallize chromium or molybdenum or tungsten still exists in an amorphous form.

[0079] Preferably, the electrodeposition method in step (1) refers to a constant potential deposition or cyclic voltammetry deposition method; the deposition potential of the constant potential deposition is -1.0 to 1.5 V vs. Hg / HgO, and the deposition time is 300 to 1100 s; the potential range of the cyclic voltammetry deposition is -1.2 to -1.6 V vs. Hg / HgO, and the deposition time is 60 to 100 min.

[0080] Preferably, the nickel-chromium plating solution formula in step (1) is: 1 g of NiSO4·6H2O, 1 g of NiCl2·6H2O, 9.6 g of CrCl3·6H2O, 7.7 g of C6H8O7, 10.7 g of Na3C6H5O7, 6.2 g of H3BO3, 0.02 g of CH3(CH2) 11OSO3Na and 100 mL deionized water. The nickel-molybdenum plating solution formula is: 3 g Na2MoO4·2H2O, 6 g NiSO4·6H2O, 2 mL NH3·H2O, 8 g Na3C6H5O7·2H2O, 2 g NiCl·6H2O and 100 mL deionized water. The nickel-tungsten plating solution formula is: 2.6 g NiSO4·6H2O, 0.48 g NiCl2·6H2O, 6.6-19.8 g Na2WO4·2H2O, 12.9 g Na3C6H5O7, 3.1 g H3BO3 and 100 mL deionized water.

[0081] The application direction of the nickel-based compound-amorphous chromium group heterojunction self-supporting electrode prepared by the above method is: electrocatalytic hydrogen evolution reaction, applied to an electrocatalyst for hydrogen evolution reaction, which can improve the HER catalytic efficiency and durability in electrolyte.

[0082] In order to better understand the essence of the present application, the present application is further described below in combination with 15 examples: Example 1: Preparation, characterization and performance test of trinickel nitride-amorphous molybdenum / carbon cloth (Ni3N-a-Mo / CC-700)

[0083] (1) Preparation, characterization and test of amorphous nickel-molybdenum / carbon cloth (Ni-Mo / CC-700)

[0084] The carbon cloth was cut into a 2 cm*1 cm rectangle, immersed in a mixed solution of 10% nitric acid and 10% sulfuric acid (volume ratio of nitric acid to sulfuric acid 3:1) for 12 h, then washed with deionized water until the washing liquid was neutral, and dried at 40°C for 8 h for standby. The Ni-Mo / CC precursor was prepared by constant potential deposition method. During the synthesis process, the pretreated carbon cloth was used as the working electrode, the Hg / HgO electrode (1 mol L -1 KOH solution) was used as the reference electrode, and the carbon rod was used as the counter electrode. The electrolyte was composed of 3 g Na2MoO4·2H2O, 6 g NiSO4·6H2O, 2 mL NH3·H2O, 8 g Na3C6H5O7·2H2O, 2 g NiCl·6H2O and 100 mL deionized water. By constant potential method, the deposition was carried out at-1.5 V vs. Hg / HgO for 700 s. After deposition, the working electrode was washed with deionized water and dried in an oven at 40°C for 8 h. According to the electrodeposition time, the sample was marked as Ni-Mo / CC-700.

[0085] Figure 1 For the SEM image of Ni-Mo / CC-700, it can be seen that the carbon cloth fiber surface is uniformly covered with a nickel-molybdenum plating layer; Figure 2Fig. a is a TEM image, and Fig. b is a selected area electron diffraction result, and no lattice fringes and crystalline diffraction patterns are found, proving that the surface coating is indeed amorphous; Figure 3 Fig. is an XRD spectrum, and only two steamed bun peaks of the carbon cloth substrate are observed, and no other crystalline diffraction peaks are observed; Figure 4 Fig. is an HER polarization curve of Ni-Mo / CC-700, and the overpotential at 10 mA cm-2is 132 mV. -2 Fig. is an HER polarization curve of Ni-Mo / CC-700, and the overpotential at 10 mA cm-2is 132 mV.

[0086] (2) Preparation, characterization and performance test of triniickel nitride-amorphous molybdenum / carbon cloth (Ni3N-a-Mo / CC-700)

[0087] The Ni-Mo / CC-700 obtained in step (1) is placed in a quartz boat, and the quartz boat is placed in a tube furnace, and is heated to 500°C in ammonia, and is kept for 2 h, and the amorphous nickel on the surface of the carbon cloth is converted into triniickel nitride nanocrystals, and the difficult-to-crystallize molybdenum still exists in an amorphous form, thereby obtaining Ni3N-a-Mo / CC-700.

[0088] Figure 5 Fig. is a SEM image, and it can be seen that the coating after the nitriding treatment still uniformly covers the surface of the carbon cloth fiber; Figure 6 Fig. is a high-magnification TEM image, and the crystalline and amorphous regions are clearly visible, the crystalline region has a size of 5-10 nm, and the composition is Ni3N, and the amorphous region is amorphous Mo (a-Mo); Figure 7 The selected area electron diffraction of Fig. further proves that the crystal structure of the crystalline part corresponds to the Ni3N phase; Figure 8 Fig. is an XRD spectrum, and the signal is well matched with the standard signal of Ni3N (PDF #89-5144); Figure 9 Fig. a of Fig. is an XPS full spectrum of the Ni3N-a-Mo / CC-700 catalyst, which confirms the existence of Ni, Mo, C, N and O elements, and the O element is attributed to the surface oxidation after exposure to air. Figure 9 Fig. b of Fig. is a Ni 2p fine spectrum, and different valence states of Ni 2p 3 / 2 , Ni 2p 1 / 2 and the corresponding satellite peaks can be fitted; Figure 9 Fig. c of Fig. is a Mo 3d fine spectrum, and different oxidation states of Mo 3+ (229.29 eV and 232.69 eV), Mo 5+ (230.29.3 eV and 233.99 eV) and Mo 6+ (232.09 eV and 235.49 eV) can be fitted, which are formed due to surface oxidation. Figure 9The d map in the figure is a fine spectrum of N1s, the peak at 399.39 eV corresponds to N-H group, and the fitting peaks of N1s at 395.29 eV and 397.59 eV are close to Mo-N bond and Ni-N bond respectively; Figure 10 The figure is the HER polarization curve of Ni3N-a-Mo / CC-700, and a 10 mA cm-2 current density can be obtained with a 70 mV overpotential, indicating excellent electrocatalytic hydrogen evolution performance; -2 The figure is the time-current curve at a 70 mV overpotential, and it can be seen that the current of the catalytic electrode almost does not decay after 20 h of continuous work, proving excellent stability. Figure 11 The figure is the time-current curve at a 70 mV overpotential, and it can be seen that the current of the catalytic electrode almost does not decay after 20 h of continuous work, proving excellent stability.

[0089] Example 2: Preparation, characterization and performance test of triniickel nitride-amorphous molybdenum / carbon cloth (Ni3N-a-Mo / CC-300)

[0090] All experimental procedures and parameters in this example are the same as those in Example 1, and the only difference is that in step (1), the deposition time at a potential of -1.5 V vs. Hg / HgO is changed from 700 s to 300 s. Figure 12 The figure is the SEM image of the precursor Ni-Mo / CC-300, and it can be seen from the position of the coating rupture that the thickness of the amorphous Ni-Mo thin layer is about 0.2-0.5 microns; Figure 13 The figure is the HER polarization curve, and the overpotential at a 10 mA cm-2 current density is 256 mV. -2 After conversion by annealing in ammonia, the HER performance of the obtained Ni3N-a-Mo / CC-300 is also lower than that of Ni3N-a-Mo / CC-700, because the deposition time is too short and the thickness of the thin layer is too small, and the active ingredients are insufficient.

[0091] Example 3: Preparation, characterization and performance test of triniickel nitride-amorphous molybdenum / carbon cloth (Ni3N-a-Mo / CC-1100)

[0092] All experimental procedures and parameters in this example are the same as those in Example 1, and the only difference is that in step (1), the deposition time at a potential of -1.5 V vs. Hg / HgO is changed from 700 s to 1100 s. Figure 14 The figure is the SEM image of the precursor Ni-Mo / CC-1100, and it can be seen from the position of the coating rupture that the thickness of the amorphous Ni-Mo thin layer is about 0.5-1 micron; Figure 15 The figure is the HER polarization curve, and the overpotential at a 10 mA cm-2 current density is 256 mV. -2The overpotential at that time was 210mV. After annealing and conversion in ammonia, the HER performance of the obtained Ni3N-a-Mo / CC-1100 was also lower than that of Ni3N-a-Mo / CC-700. This is because the deposition time was too long, the thin layer was too thick, and the conductivity was reduced.

[0093] Example 4: Nickel sulfide-amorphous molybdenum / carbon cloth (NiS) x Preparation, characterization, and performance testing of α-Mo / CC:

[0094] In this embodiment, all experimental procedures and parameters are the same as in Embodiment 1. The only difference is that in step (2), "Place Ni-Mo / CC-700 in a quartz boat, place the quartz boat in a tube furnace, and heat it to 500°C in ammonia to convert the amorphous nickel on the surface of the carbon cloth into nickel nitride nanocrystals", is changed to "Place Ni-Mo / CC-700 downstream of the quartz boat, place 0.1g of sublimed sulfur upstream; place the quartz boat in a tube furnace, heat it to 500°C in argon, and hold it for 2 hours to convert the amorphous nickel on the surface of the carbon cloth into nickel sulfide", while molybdenum still exists in amorphous form. Figure 16 NiS x SEM images of -a-Mo / CC show that the thin layer still uniformly covers the surface of the carbon fiber after vulcanization. Figure 17 The XRD pattern clearly shows the diffraction peaks of NiS and NiS2, indicating that amorphous nickel has been transformed into nickel sulfide nanocrystals. No diffraction peaks of Mo were observed, indicating that Mo still exists in an amorphous form. Figure 18 NiS x HER polarization curves of -a-Mo / CC, 10 mA cm⁻¹ -2 The overpotential at this time is 123mV, indicating good HER catalytic activity.

[0095] Example 5: Preparation, characterization, and performance testing of nickel diselenide-amorphous molybdenum / carbon cloth (NiSe2-a-Mo / CC):

[0096] In this embodiment, all experimental procedures and parameters are the same as in Embodiment 1. The only difference is that in step (2), "Place Ni-Mo / CC-700 on a quartz boat, place the quartz boat in a tube furnace, and heat it to 500°C in ammonia to convert the amorphous nickel on the surface of the carbon cloth into nickel diselenide nanocrystals", is changed to "Place Ni-Mo / CC-700 downstream of the quartz boat, place 0.1g of selenium powder upstream; place the quartz boat in a tube furnace, heat it to 500°C in argon, and hold it for 2 hours to convert the amorphous nickel on the surface of the carbon cloth into nickel diselenide", while molybdenum still exists in an amorphous form. Figure 19 The image shows a SEM image of NiSe2-a-Mo / CC, which shows that the thin layer after selenization still uniformly covers the surface of the carbon cloth fiber. Figure 20For XRD spectrum, it is proved that amorphous Ni is converted to NiSe2nanocrystals, and there is no diffraction peak of Mo, indicating that Mo still exists in amorphous form; Figure 21 For the HER polarization curve of NiSe2-a-Mo / CC, the overpotential is 139 mV at 10 mA cm-2, and it has good HER catalytic activity. -2

[0097] Example 6: Preparation, characterization and performance test of nickel phosphide-amorphous molybdenum / carbon cloth (Ni2P-a-Mo / CC)

[0098] In this embodiment, all experimental procedures and parameters are the same as in Example 1, the only difference is that in step (2) “place Ni-Mo / CC-700 in a quartz boat, place the quartz boat in a tube furnace, and heat to 500℃ in ammonia, convert the amorphous nickel on the surface of the carbon cloth to nitride nickel nanocrystals,” is changed to “place Ni-Mo / CC-700 in the downstream of the quartz boat, place 0.1g sodium hypophosphite in the upstream; place the quartz boat in a tube furnace, heat to 500℃ in argon, and keep for 2h, convert the amorphous nickel on the surface of the carbon cloth to nickel phosphide,” while molybdenum still exists in amorphous form. Figure 22 For the SEM image of Ni2P-a-Mo / CC, it can be seen that the thin layer still uniformly covers the surface of the carbon cloth fiber after phosphating; Figure 23 For XRD spectrum, it is proved that amorphous Ni is converted to Ni2P nanocrystals, and there is no diffraction peak of Mo, indicating that Mo still exists in amorphous form; Figure 24 For the HER polarization curve of Ni2P-a-Mo / CC, the overpotential is 160 mV at 10 mA cm-2, and it has good HER catalytic activity. -2

[0099] Example 7: Preparation, characterization and performance test of nickel oxide-amorphous molybdenum / carbon cloth (NiO-a-Mo / CC):

[0100] In this embodiment, all experimental procedures and parameters are the same as in Example 1, the only difference is that in step (2) heating to 500℃ in ammonia is changed to heating to 500℃ in air, and keeping for 2h, convert the amorphous nickel on the surface of the carbon cloth to nickel oxide, while molybdenum still exists in amorphous form. Figure 25 For the SEM image of NiO-a-Mo / CC, it can be seen that the surface of the thin layer becomes rough and grows sharp structures after oxidation; Figure 26 For XRD spectrum, it is proved that amorphous Ni is oxidized to NiO nanocrystals, while Mo still exists in amorphous form; Figure 27 For the HER polarization curve of NiO-a-Mo / CC, the overpotential is 228 mV at 10 mA cm-2, and the HER catalytic activity is poor. -2 ​​​

[0101] Example 8: Preparation, characterization and performance test of triniickel- amorphous tungsten / carbon cloth (Ni3N-a-Mo / CC-0.4)

[0102] (1) Preparation, characterization and test of amorphous nickel-tungsten / carbon cloth (Ni-W / CC-0.4)

[0103] The carbon cloth was cut into a 2 cm * 1 cm rectangle, immersed in a mixed solution of 10% nitric acid and 10% sulfuric acid (volume ratio of nitric acid to sulfuric acid 3:1) for 12 h; then washed with deionized water until the washing liquid was neutral, and dried at 40°C for 8 h for standby; the Ni-W / CC precursor was prepared by cyclic voltammetric deposition, and during the synthesis, the pretreated carbon cloth was used as the working electrode, the Hg / HgO electrode (1 mol L -1 KOH solution) was used as the reference electrode, and the carbon rod was used as the counter electrode. The electrolyte was prepared from 2.6 g of NiSO4·6H2O, 0.48 g of NiCl2·6H2O, 13.2 g of Na2WO4·2H2O, 12.9 g of Na3C6H5O7, 3.1 g of H3BO3 and 100 mL of deionized water. By cyclic voltammetry, a potential range of -1.2 to -1.6 V vs. Hg / HgO was used, a scan rate of 50 mV s -1 -1 was used, and the deposition time was 60 min. After deposition, the working electrode was washed with deionized water and dried in an oven at 40°C for 8 h. According to the concentration of Na2WO4·2H2O in the electrolyte (0.4 mol L -1 -1), the sample was labeled as Ni-W / CC-0.4.

[0104] Figure 28 Fig. a in the figure is a SEM image of Ni-W / CC-0.4, Figure 28 Fig. b is a further magnified SEM image, which shows that the Ni-W coating uniformly covers the surface of the carbon cloth fiber; Figure 29 Fig. a is a TEM image of the thin layer, Figure 29 Fig. b is the corresponding selected area electron diffraction pattern, which proves that the Ni-W thin layer obtained by electrodeposition is amorphous; Figure 30 is an XRD spectrum, only the signal of the carbon cloth substrate is seen, and no other crystalline diffraction peaks are seen; Figure 31 is the HER polarization curve of Ni-W / CC-0.4, the overpotential at 10 mA cm -2 -1 is 127 mV, which shows that the precursor has already exhibited good HER catalytic activity.

[0105] (2) Preparation, characterization and performance test of triniickel- amorphous tungsten / carbon cloth (Ni3N-a-Mo / CC-0.4)

[0106] The Ni-W / CC-0.4 obtained in step (1) was placed in a quartz boat, which was placed in a tube furnace, and heated to 500℃ in ammonia for 2h. The amorphous nickel on the surface of the carbon cloth was converted into nanocrystalline Ni3N, while still existing in an amorphous form, thereby obtaining Ni3N-a-W / CC-0.4.

[0107] Figure 32 Fig. a in 32 and Fig. b in 32 are low and high magnification SEM images of the sample, respectively, and it can be seen that the thin layer still uniformly covers the surface of the carbon cloth fibers after nitriding; Figure 33 Fig. a in 32 is a TEM image of the thin layer, which directly confirms the existence of the crystalline-amorphous structure, and the crystal lattice fringes in the crystalline region correspond to Ni3N, Figure 33 Fig. b in 32 is a selected area electron diffraction pattern, which further confirms the existence of Ni3N. Figure 34 Fig. 33 is an XRD spectrum, and in addition to the signal of the carbon cloth, the other diffraction peaks are consistent with the standard card of the Ni3N phase; Figure 35 Fig. a in 34 is an XPS full spectrum of Ni3N-a-W / CC-0.4, Figure 35 Fig. b in 34 is a Ni 2p fine spectrum, which can be fitted into different valence states of Ni2p 1 / 2 , Ni2p 3 / 2 and the corresponding satellite peaks. Figure 35 Fig. c in 34 is a W 4f fine spectrum, which can be fitted into the oxidation states of W 6+ (36.88 and 39.6eV), and the two pairs of peaks of W-O bond (37.6ev) and (35.4eV), which is because the surface oxidation inevitably occurs when the material is exposed to air. Figure 35 Fig. d in 34 is a N1s fine spectrum, and the peak at 399.39eV corresponds to N-H groups, and the fitted peaks of N1s at 395.29eV and 398eV are close to W-N bond and Ni-N bond, respectively; Figure 36 Fig. 35 is a HER polarization curve of Ni3N-a-W / CC-0.4, and the overpotential at 10mA cm -2 is 70mV, which exhibits excellent HER catalytic activity; Figure 37 Fig. 36 is a time-current curve of Ni3N-a-W / CC-0.4 at an overpotential of 70mV, and it can be seen that the current of the catalytic electrode hardly decays after 20h of continuous work, which proves its excellent stability.

[0108] Example 9: Preparation, characterization and performance test of Ni3N-a-W / CC-0.2

[0109] All experimental procedures and parameters in this embodiment are the same as in Embodiment 8. The only difference is that in step (1), the 13.2g Na2WO4·2H2O in the electrolyte used for electrodeposition is replaced with 6.6g Na2WO4·2H2O, corresponding to a concentration of 0.2mol / L. -1 . Figure 38 Here is the HER polarization curve of the precursor Ni-W / CC-0.2, 10 mA cm⁻¹ -2 The overpotential was 186 mV. After annealing and conversion in ammonia, the HER performance of the obtained Ni3N-aW / CC-0.2 was also lower than that of Ni3N-aW / CC-0.4. This is because the W content was too low, and the synergistic effect of the prepared crystalline-amorphous heterostructure was not optimal.

[0110] Example 10: Preparation, characterization and performance testing of nickel nitride-amorphous tungsten / carbon cloth (Ni3N-aW / CC-0.6)

[0111] In this embodiment, all experimental procedures and parameters are the same as in Example 8. The only difference is that in step (1), the 13.2g Na2WO4·2H2O in the electrolyte used for electrodeposition is replaced with 19.8g Na2WO4·2H2O, corresponding to a concentration of 0.6mol / L. -1 . Figure 39 Here are the HER polarization curves of the precursor Ni-W / CC-0.6, 10 mA cm⁻¹ -2 The overpotential was 144 mV. After annealing and conversion in ammonia, the HER performance of the obtained Ni3N-aW / CC-0.6 was also lower than that of Ni3N-aW / CC-0.4. This is because the W content was too high, and the synergistic effect of the prepared crystalline-amorphous heterostructure was not optimal.

[0112] Example 11: Nickel sulfide-amorphous tungsten / carbon cloth (NiS) x Preparation, characterization and performance testing of -aW / CC)

[0113] In this embodiment, all experimental procedures and parameters are the same as in embodiment 8. The only difference is that in step (2), Ni-W / CC-0.4 was placed on a quartz boat and the quartz boat was placed in a tube furnace and heated to 500°C in ammonia. Instead, Ni-W / CC-0.4 was placed downstream of the quartz boat and 0.1g of sublimed sulfur was placed upstream. The quartz boat was placed in a tube furnace and heated to 500°C in argon and held for 2 hours to convert the amorphous nickel on the carbon cloth surface into nickel sulfide, while tungsten still exists in amorphous form. Figure 40 The image shows a SEM image of NiS-aW / CC, which shows that the thin layer is still uniformly covered after sulfurization. Figure 41For the XRD pattern of NiS-a-W / CC, the diffraction peaks of NiS and NiS2 are clearly visible, indicating that amorphous nickel is converted into nickel sulfide nanocrystals, and no diffraction peak of W is visible, indicating that W still exists in amorphous form; Figure 42 For the XRD pattern of NiS-a-W / CC, the diffraction peaks of NiS and NiS2 are clearly visible, indicating that amorphous nickel is converted into nickel sulfide nanocrystals, and no diffraction peak of W is visible, indicating that W still exists in amorphous form; x For the HER polarization curve of NiS-a-W / CC, the overpotential at 10 mA cm-2 is 130 mV, which has good HER catalytic activity. -2 For the XRD pattern of NiS-a-W / CC, the diffraction peaks of NiS and NiS2 are clearly visible, indicating that amorphous nickel is converted into nickel sulfide nanocrystals, and no diffraction peak of W is visible, indicating that W still exists in amorphous form;

[0114] Example 12: Preparation, characterization and performance test of nickel diselenide-amorphous tungsten / carbon cloth (NiSe2-a-W / CC)

[0115] In this example, all experimental procedures and parameters are the same as in Example 8, the only difference is that in step (2), Ni-W / CC-0.4 is placed in the quartz boat, the quartz boat is placed in the tube furnace, and the temperature is raised to 500℃ in ammonia, which is changed to placing Ni-W / CC-0.4 downstream of the quartz boat, and placing 0.1g of selenium powder upstream; the quartz boat is placed in the tube furnace, and the temperature is raised to 500℃ in argon, and the temperature is kept for 2h, converting the amorphous nickel on the surface of the carbon cloth into nickel diselenide, while the tungsten still exists in amorphous form. Figure 43 For the SEM image of NiSe2-a-W / CC, it can be seen that the thin layer after selenium is still uniformly covered on the surface of the carbon cloth fiber; Figure 44 For the XRD pattern, it is proved that amorphous Ni is converted into NiSe2 nanocrystals, and no diffraction peak of W is visible, indicating that W still exists in amorphous form; Figure 45 For the HER polarization curve of NiSe2-a-W / CC, the overpotential at 10 mA cm-2 is 165 mV, which has good HER catalytic activity. -2 For the XRD pattern, it is proved that amorphous Ni is converted into NiSe2 nanocrystals, and no diffraction peak of W is visible, indicating that W still exists in amorphous form;

[0116] Example 13: Preparation, characterization and performance test of nickel phosphide-amorphous tungsten / carbon cloth (Ni2P-a-W / CC)

[0117] In this example, all experimental procedures and parameters are the same as in Example 8, the only difference is that in step (2), Ni-W / CC-0.4 is placed in the quartz boat, the quartz boat is placed in the tube furnace, and the temperature is raised to 500℃ in ammonia, which is changed to placing Ni-W / CC-0.4 downstream of the quartz boat, and placing 0.1g of sodium hypophosphite upstream; the quartz boat is placed in the tube furnace, and the temperature is raised to 500℃ in argon, and the temperature is kept for 2h, converting the amorphous nickel on the surface of the carbon cloth into nickel phosphide, while the tungsten still exists in amorphous form. Figure 46 For the SEM image of Ni2P-a-W / CC, it can be seen that the thin layer after phosphating is still uniformly covered on the surface of the carbon cloth fiber; Figure 47 For the XRD pattern, it is proved that amorphous Ni is converted into Ni2P nanocrystals, and no diffraction peak of W is visible, indicating that W still exists in amorphous form;Figure 48 HER polarization curve of Ni2P-a-Mo / CC, 10 mA cm-2 -2 The overpotential at 10 mA cm-2 is 185 mV, which has good HER catalytic activity.

[0118] Example 14: Preparation, characterization and performance test of nickel oxide-amorphous tungsten / carbon cloth (NiO-a-W / CC)

[0119] All experimental procedures and parameters in this example are the same as those in Example 8, the only difference is that in step (2), the temperature is raised to 500°C in ammonia instead of being raised to 500°C in air for 2 h, which converts the amorphous nickel on the surface of the carbon cloth into nickel oxide, while the tungsten still exists in the amorphous form. Figure 49 The SEM image of NiO-a-W / CC is shown, which shows that the surface of the thin layer becomes rough and grows spikes after oxidation; Figure 50 The XRD spectrum shows that the amorphous Ni is oxidized to NiO nanocrystals, while the W still exists in the amorphous form; Figure 51 The HER polarization curve of NiO-a-W / CC is shown, 10 mA cm-2 -2 The overpotential at 10 mA cm-2 is 329 mV, which has poor HER catalytic activity.

[0120] Example 15: Preparation, characterization and performance test of triniickel nitride-amorphous chromium / carbon cloth (Ni3N-a-Cr / CC)

[0121] (1) Preparation, characterization and test of amorphous nickel-chromium / carbon cloth (Ni-Cr / CC)

[0122] The carbon cloth was cut into a 2 cm*1 cm rectangle, and then immersed in a mixed solution of 10% nitric acid and 10% sulfuric acid (volume ratio of nitric acid to sulfuric acid is 3:1) for 12 h; then washed with deionized water until the washing liquid was neutral, and dried at 40°C for 8 h for standby; the Ni-Cr / CC precursor was prepared by constant potential deposition, and during the synthesis, the pretreated carbon cloth was used as the working electrode, the Hg / HgO electrode (1 mol L -1 KOH solution) was used as the reference electrode, and the carbon rod was used as the counter electrode. The electrolyte was prepared by dissolving 1 g of NiSO4·6H2O, 1 g of NiCl2·6H2O, 9.6 g of CrCl3·6H2O, 7.7 g of C6H8O7, 10.7 g of Na3C6H5O7, 6.2 g of H3BO3, 0.02 g of CH3(CH2) 11 OSO3Na and 100 mL of deionized water. By constant potential deposition, the working electrode was deposited at -1.5 V vs. Hg / HgO for 1000 s. After deposition, the working electrode was washed with deionized water and dried in an oven at 40°C for 8 h. Figure 52For the SEM image of the obtained Ni-Cr / CC, it can be seen that the coating uniformly covers the surface of the carbon cloth fiber.

[0123] (2) Preparation, characterization and performance test of triniickel-nanocrystalline chromium / carbon cloth (Ni3N-a-Cr / CC)

[0124] The Ni-Cr / CC obtained in step (1) was placed in a quartz boat, and the quartz boat was placed in a tube furnace. The temperature was raised to 500℃ in ammonia, and the temperature was kept for 2h. The amorphous nickel on the surface of the carbon cloth was converted into triniickel nanocrystals, while the chromium still existed in the amorphous form, thereby obtaining Ni3N-a-Cr / CC-. Figure 53 For the XRD spectrum of the obtained Ni3N-a-Cr / CC, in addition to the signal of the carbon cloth, the other diffraction peaks are consistent with the standard card of Ni3N phase, proving that the amorphous Ni in the coating is converted into Ni3N nanocrystals, and there are no diffraction peaks of W and its compounds in the XRD spectrum, indicating that W still exists in the amorphous form; Figure 54 For the HER polarization curve graph, the overpotential at 10mAcm-2is 71mV, showing excellent HER electrocatalytic activity. -2 ​

Claims

1. A nickel-based compound-amorphous chromium family heterojunction self- supporting electrode characterized by: It is composed of nickel-based compound nanocrystal-amorphous chromium family heterojunction thin layer covering on carbon cloth fiber, the nickel-based compound component is nickel disulfide or nickel sulfide or nickel diselenide or phosphide two nickel or three nickel nitride or nickel oxide, and the amorphous chromium family component is chromium or molybdenum or tungsten.

2. The nickel-based compound-amorphous chromium family heterojunction self-supported electrode according to claim 1, characterized in that: The thickness of the thin layer is 0.2-1 microns, and the nanocrystal size is 5-10 nanometers.

3. A method for preparing the nickel-based compound-amorphous chromium heterojunction self-supporting electrode according to claim 1, characterized in that: It comprises the following steps: (1) first introduce active groups on the surface of carbon cloth fiber, then wash with deionized water until the washing liquid is neutral, and dry; (2) a layer of amorphous nickel-chromium or nickel-molybdenum or nickel-tungsten thin layer is covered on the surface of the dried carbon cloth fiber by using electrodeposition method with nickel-chromium plating solution or nickel-molybdenum plating solution or nickel-tungsten plating solution as electrolyte, to obtain amorphous nickel-chromium family metal / carbon cloth; The electrodeposition method is constant potential deposition or cyclic voltammetry deposition method, the deposition potential of constant potential deposition is-1.0-1.5 V vs. Hg / HgO, and the deposition time is 300-1100 s; the potential range of cyclic voltammetry deposition is-1.2--1.6 V vs. Hg / HgO, and the deposition time is 60-100 min; The formula of the nickel-chromium plating solution is: 1 g of NiSO4-6H2O, 1 g of NiCl2-6H2O, 9.6 g of CrCl3-6H2O, 7.7 g of C6H8O7, 10.7 g of Na3C6H5O7, 6.2 g of H3BO3, 0.02 g of CH3(CH2) 11 OSO3Na, and 100 mL of deionized water. The formula of the nickel-chromium plating solution is: 1 g of NiSO4-6H2O, 1 g of NiCl2-6H2O, 9.6 g of CrCl3-6H2O, 7.7 g of C6H8O7, 10.7 g of Na3C6H5O7, 6.2 g of H3BO3, 0.02 g of CH3(CH2) <000 The formula of the nickel-molybdenum plating solution is: 3 g Na2MoO4·2H2O, 6 g NiSO4·6H2O, 2 mL NH3·H2O, 8 g Na3C6H5O7·2H2O, 2 g NiCl·6H2O and 100 mL deionized water; The formula of the nickel-tungsten plating solution is 2.6 g NiSO4·6H2O, 0.48 g NiCl2·6H2O, 6.6-19.8 g Na2WO4·2H2O, 12.9 g Na3C6H5O7, 3.1 g H3BO3 and 100 mL deionized water; (3) Place the amorphous nickel-chromium family metal / carbon cloth downstream of the quartz boat, place sublimation sulfur or selenium powder or sodium hypophosphite upstream of the quartz boat, then place the quartz boat in a tube furnace, heat and keep warm in nitrogen or argon, convert the amorphous nickel on the surface of the carbon cloth into nickel disulfide or nickel sulfide or nickel diselenide or phosphide two nickel nanocrystals, and chromium or molybdenum or tungsten still exists in amorphous form; Or: Place the amorphous nickel-chromium family metal / carbon cloth in the quartz boat, place the quartz boat in a tube furnace, heat and keep warm in ammonia or air, convert the amorphous nickel on the surface of the carbon cloth into three nickel nitride or nickel oxide nanocrystals, and chromium or molybdenum or tungsten still exists in amorphous form.

4. The method of claim 3 wherein: In step (1), the carbon cloth is soaked in a mixed solution of nitric acid or sulfuric acid or sulfuric acid and nitric acid with a mass fraction of 10%-15% to introduce active groups on the fiber surface.

5. The method of claim 3 wherein: In step (3), the temperature of heating is 450-500℃, and the time of keeping warm is 1-3h.

6. The method of claim 3 wherein: In step (3), the ratio of the mass of the sublimed sulfur or selenium powder or sodium hypophosphite to the area of the amorphous nickel-chromium group metal / carbon cloth is 0.05 to 0.1 g cm -2 .

7. Use of the nickel-based compound-amorphous chromium family heterojunction self- supporting electrode according to claim 1, characterized by the fact that: It is applied to hydrogen evolution reaction electrocatalyst.

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