A compact high efficiency oxyhydrogen generator cell and method with adjustable gas production

Abstract

The application discloses a compact high-efficiency hydrogen-oxygen generator electrolytic cell with adjustable gas production and a method; the two ends of a cylinder body are sealed by end covers; the cylinder body is divided into multiple independent sealed electrolytic chambers by multiple insulating partitions; a water outlet is formed in the upper end cover and is communicated with the independent sealed electrolytic chambers; a water inlet is formed in the lower end cover and is communicated with the independent sealed electrolytic chambers; a pair of electrode groups are arranged in each sealed electrolytic chamber; the sealed electrolytic chamber serves as an electrolytic cell; when the electrolytic cell works, electrolyte flows into the sealed electrolytic chambers through the water inlet, and hydrogen-oxygen mixed gas and electrolyte flow out of the sealed electrolytic chambers through the water outlet. The application realizes the increase of the adjustable gas production and the maximum gas production by optimizing the structural design of the electrolytic cell and replacing the high-efficiency electrode material, and has the characteristics of high efficiency, stability and easy scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to an alkaline water electrolysis hydrogen-oxygen generator electrolyzer, in particular to a compact high-efficiency hydrogen-oxygen generator electrolyzer with adjustable gas production and a method. BACKGROUND

[0002] In the traditional automobile industry, non-renewable fossil energy such as gasoline or diesel is commonly used as fuel to drive internal combustion engines. However, due to overexploitation, non-renewable fossil energy will eventually face the dilemma of depletion, leading to an energy crisis.

[0003] In addition, during the process of converting chemical energy of fossil energy into kinetic energy in the automobile internal combustion engine, the energy conversion efficiency is low. According to relevant research and measurement at home and abroad, the direct fuel efficiency of the mainstream mass-produced automobile internal combustion engine is about 30-40%, and only a few mass-produced engines using supercharging technology can reach about 40-50%.

[0004] Therefore, the internal combustion engine is a relatively low-efficiency mechanical device: only 1 / 3 of the energy contained in the fuel is converted into mechanical energy by the internal combustion engine to drive the automobile to run. The low energy conversion efficiency increases the amount of energy used, further exacerbating the energy crisis.

[0005] In addition, due to incomplete combustion of fuel, automobile exhaust emissions also cause serious environmental pollution problems. Automobile exhaust emissions mainly include CO, NO x and HC and particulate matter of harmful components.

[0006] Although new energy vehicles represented by lithium-ion batteries bring hope to solve the energy crisis and environmental pollution problems, a series of drawbacks such as insufficient infrastructure, range anxiety, poor safety, and pollution caused by waste batteries still restrict the development of new energy vehicles and constrain their large-scale popularization. Therefore, at the present stage, how to reduce the use of fossil energy, improve the efficiency of the internal combustion engine, or improve the fuel efficiency is a key technology to solve the above problems.

[0007] Studies have shown that hydrogen has the characteristics of fast flame propagation speed (7.7 times that of gasoline) and low minimum ignition energy (1 / 3 of that of gasoline), and a hydrogen-doped fuel internal combustion engine can utilize these unique physical and chemical properties of hydrogen to improve the oxidation path of fossil fuels and optimize the turbulent flame structure, thereby achieving efficient (combustion efficiency can be increased to 70-90%), clean and stable combustion of fossil fuels. Therefore, using a compact on-board hydrogen-oxygen generator to intelligently allocate and control the electrical energy output by the on-board generator, using the surplus electrical energy of the storage battery to electrolyze water, and generating hydrogen-oxygen mixed gas in real time to be fed into the engine and burned with gasoline can significantly improve the conversion efficiency between fuel chemical energy and automobile mechanical energy, while reducing air pollution caused by exhaust gas.

[0008] Based on the above theory, Chinese invention patent CN201911408794.4 discloses a compact hydrogen-oxygen generator: through the compact design of tightly nested anode porous electrode rod and cathode stainless steel sleeve, high-efficiency electrolysis is realized, and the volume and weight of the electrolytic cell are reduced under the premise of meeting the gas production size; in the preparation of the porous electrode, dealloying is used to realize the porosity of the iron-based alloy, and the porous iron-based alloy rod is used as the electrode material. The characteristics of high specific surface area of porous materials can be utilized to realize the miniaturization and simplification of the electrolytic cell of the vehicle-mounted hydrogen-oxygen generator while ensuring the size of the gas production.

[0009] However, there are still some key problems in this invention: first, due to the single electrolytic chamber design of the electrolytic cell, the hydrogen-oxygen generator cannot flexibly adjust the gas production size according to the actual application scene, and the structure of the electrolytic cell needs to be further optimized. Second, the high specific surface area porous electrode used in the electrolytic cell of the hydrogen-oxygen generator is not loaded with high intrinsic catalytic activity catalyst, and the gas production is bottlenecked, which is difficult to further improve. Therefore, in recent years, researchers have been committed to developing transition metal-based catalysts with high intrinsic catalytic activity and loading them on the surface of the porous electrode to improve the electrolysis efficiency. Among them, transition metal borides have the characteristics of environmental friendliness, low cost, good electrical conductivity and good catalytic activity, and have been widely favored by the industry.

[0010] Chinese invention patent CN201810011644.9 discloses a preparation method of transition metal boride catalyst: using a solid boronizing agent to coat the transition metal, and performing boronizing treatment by programmed temperature heating, wherein the boronizing agent is composed of essential boronizing medium, non-essential activator and non-essential filler. By this solid phase boronizing method, the synthesis of corresponding metal boride catalyst on metal sheet can be realized directly, which is beneficial to large-scale preparation.

[0011] However, the intrinsic catalytic activity of the transition metal boride catalyst prepared by this invention is still not ideal. In 1 mole per liter of KOH electrolyte, the current density under the geometric area is 10 mAcm -2 , and the required overpotential is as high as 300-400 mV. Moreover, the catalyst does not exhibit long stability under harsh working conditions with a current density exceeding 1000 mAcm -2 . Therefore, in view of practical application, the improvement of the comprehensive performance of transition metal boride catalysts still has a long way to go.

[0012] In summary, in order to better promote the practical application of vehicle-mounted hydrogen-oxygen generators, it is urgent to further optimize the structure of the hydrogen-oxygen generator electrolytic cell and develop transition metal boride catalysts with high intrinsic catalytic activity and long stability under harsh working conditions. SUMMARY

[0013] To solve the key technical problems that the existing compact hydrogen-oxygen generator cannot flexibly adjust the gas production according to the actual application scene and the gas production is difficult to further improve, the application provides a compact high-efficiency hydrogen-oxygen generator electrolytic cell and method with adjustable gas production.

[0014] The application divides the single electrolytic chamber of the original electrolytic cell into several (six) sealed electrolytic chambers 91 by adding insulation partitions, places one boronized porous electrode rod as an anode and one stainless steel tube as a cathode in each sealed electrolytic chamber 91, and tightly nests the two, so that the hydrogen-oxygen generator electrolytic cell can realize flexible adjustment of the gas production under the premise of compact design by changing the connection method between the sealed electrolytic chambers 91.

[0015] The application is implemented by the following technical scheme:

[0016] A compact high-efficiency hydrogen-oxygen generator electrolytic cell with adjustable gas production comprises a barrel 3, and the two ends of the barrel 3 are sealed by an upper end cover 1 and a lower end cover 2.

[0017] A plurality of insulation partitions 9 are arranged in the barrel 3; the plurality of insulation partitions 9 are combined and radially expanded, so as to divide the inside of the barrel 3 into a plurality of separate sealed electrolytic chambers 91.

[0018] A water outlet 6 is formed in the middle of the upper end cover 1; the water outlet 6 is in communication with the separate sealed electrolytic chambers 91 respectively.

[0019] A water inlet 7 is formed in the middle of the lower end cover 2; the water inlet 7 is in communication with the separate sealed electrolytic chambers 91 respectively.

[0020] A pair of electrode groups 8 are arranged in each sealed electrolytic chamber 91.

[0021] The sealed electrolytic chamber 91 serves as an electrolytic cell; when the electrolytic cell works, electrolyte flows into the sealed electrolytic chambers 91 through the water inlet 7, and the generated hydrogen-oxygen mixed gas and electrolyte flow out through the water outlet 6.

[0022] The electrode group 8 comprises an anode 4 and a cathode 5.

[0023] The cathode 5 is in a cylindrical structure, and the anode 4 is in a columnar structure; the anode 4 is sleeved in the inside of the cathode 5.

[0024] A conductive plate 51 is arranged at the end of the cathode 5 and is fixed by a bolt and extends outside the upper end cover 1 or the lower end cover 2 as a negative electrode interface of the sealed electrolytic chamber 91; and one end of the anode 4 is in a threaded rod structure, which extends out of the upper end cover 1 or the lower end cover 2 as a positive electrode interface of the sealed electrolytic chamber 91.

[0025] The negative and positive interfaces distributed on the upper end cover 1 or the lower end cover 2 are staggered in sequence, so that the positive and negative electrodes can be connected in proximity.

[0026] The anode 4 is a boronized porous electrode rod, with a diameter of 8-11.5 mm.

[0027] The cathode 5 is a stainless steel tube, which is an austenitic stainless steel rich in iron, chromium and nickel, with an inner diameter of 12-14 mm and an outer diameter of 14-16 mm.

[0028] The boronized porous electrode rod preparation method comprises the following steps:

[0029] Step one: weigh the boron supply agent, the activator, the filler and the rare earth catalyst and mix them thoroughly to obtain the boronizing agent A;

[0030] Step two: embed the porous iron-nickel alloy rod into the boronizing agent A obtained in step one to obtain the mixture B; the mass content of nickel in the porous iron-nickel alloy rod is 30-50%, and the rest is iron;

[0031] Step three: after calcination treatment of the mixture B obtained in step two, the mixture C is obtained;

[0032] Step four: take out the porous iron-nickel alloy rod in the mixture C obtained in step three, and wash and dry it to obtain the boronized porous electrode rod.

[0033] In step one, the mass ratio of the boron supply agent, the activator, the filler and the rare earth catalyst is (1-10):(1-6):(3-17):(0.2-4).

[0034] In step three, the calcination temperature of the calcination treatment is 580-1000℃, and the calcination time is 1-20 hours.

[0035] In step four, the washing refers to ultrasonic treatment with water and ethanol for 5-10 minutes; and the drying refers to drying in a drying oven for 0.2-4 hours at a drying temperature of 40-80℃.

[0036] The boron supply agent comprises boron carbide, boron iron, borax and boric anhydride, etc.

[0037] The activator comprises activated carbon, fluoroborate, carbonate and ammonium chloride, etc.

[0038] The filler comprises silicon carbide and aluminum trioxide, etc.

[0039] The rare earth catalyst comprises neodymium oxide, neodymium chloride, cerium oxide and cerium chloride, etc.

[0040] Compared with the prior art, the present application has the following advantages and effects:

[0041] (1) The present application divides multiple (six equal parts) discrete sealed electrolytic chambers 91 by using insulating partitions, and the electrode arrangement in adjacent sealed electrolytic chambers 91 is opposite. Through this simple and effective strategy, the circuit connection mode between six adjacent sealed electrolytic chambers 91 can be changed according to the actual application scene requirements, to flexibly adjust the gas production.

[0042] (2) The present application uses a simple boron-rare earth co-permeation boronizing heat treatment process to prepare boronized porous alloy rods as porous electrodes. Benefiting from the catalytic effect of rare earth elements in the boronizing process and the modulation effect on the electronic structure of metal borides, the prepared boronized porous electrode has the advantages of good stability and high intrinsic catalytic activity. Therefore, using boronized porous electrode rods as anodes can greatly improve the electrolysis efficiency while ensuring the stability and compactness of the hydrogen-oxygen generator electrolytic cell, thereby achieving the purpose of increasing the gas production.

[0043] (3) The present application realizes the adjustment of gas production and the increase of maximum gas production by optimizing the structure design of the electrolytic cell and replacing the high-efficiency electrode material, while retaining the compact structure design. It has the characteristics of high efficiency and stability, and easy to scale production. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 It is a schematic diagram of the three-dimensional structure of the hydrogen-oxygen generator electrolytic cell of the present application;

[0045] Figure 2 It is a schematic diagram of the three-dimensional structure of the upper end cover 1 of the hydrogen-oxygen generator electrolytic cell of the present application;

[0046] Figure 3 It is a schematic diagram of the three-dimensional structure of the lower end cover 2 of the hydrogen-oxygen generator electrolytic cell of the present application;

[0047] Figure 4 It is a schematic diagram of the three-dimensional structure of the insulating partition of the hydrogen-oxygen generator electrolytic cell of the present application;

[0048] Figure 5 It is an explosion view of the hydrogen-oxygen generator electrolytic cell of the present application;

[0049] Figure 6 It is a distribution diagram of the positive and negative electrode connection ports of each discrete sealed electrolytic chamber in the upper end cover 1 of the hydrogen-oxygen generator electrolytic cell of the present application;

[0050] Figure 7 It is a distribution diagram of the positive and negative electrode connection ports of each discrete sealed electrolytic chamber in the lower end cover 2 of the hydrogen-oxygen generator electrolytic cell of the present application;

[0051] Figure 8 It is a connection diagram of each discrete sealed electrolytic chamber according to circuit connection mode one;

[0052] Figure 9 Fig. 2 is a schematic diagram of the specific connection of each interface of the upper end cap 1 when connected in circuit connection mode 1;

[0053] Figure 10 Fig. 3 is a schematic diagram of the specific connection of each interface of the lower end cap 2 when connected in circuit connection mode 1;

[0054] Figure 11 Fig. 4 is a schematic diagram of the connection of each discrete sealed electrolytic chamber in circuit connection mode 2;

[0055] Figure 12 Fig. 5 is a schematic diagram of the specific connection of each interface of the upper end cap 1 when connected in circuit connection mode 2;

[0056] Figure 13 Fig. 6 is a schematic diagram of the specific connection of each interface of the lower end cap 2 when connected in circuit connection mode 2;

[0057] Figure 14 Fig. 7 is a schematic diagram of the connection of each discrete sealed electrolytic chamber in circuit connection mode 3;

[0058] Figure 15 Fig. 8 is a schematic diagram of the specific connection of each interface of the upper end cap 1 when connected in circuit connection mode 3;

[0059] Figure 16 Fig. 9 is a schematic diagram of the specific connection of each interface of the lower end cap 2 when connected in circuit connection mode 3;

[0060] Figure 17 Fig. 10 is a schematic diagram of the connection of each discrete sealed electrolytic chamber in circuit connection mode 4;

[0061] Figure 18 Fig. 11 is a schematic diagram of the specific connection of each interface of the upper end cap 1 when connected in circuit connection mode 4;

[0062] Figure 19 Fig. 12 is a schematic diagram of the specific connection of each interface of the lower end cap 2 when connected in circuit connection mode 4;

[0063] Figure 20 Fig. 13 is an X-ray diffraction pattern of the porous iron-nickel alloy rod and boronized porous alloy rod of Example 1;

[0064] Figure 21 Fig. 14 is a scanning electron microscope image of the porous iron-nickel alloy rod of Example 1, wherein (a) is an electron microscope image at 200 times magnification and (b) is an electron microscope image at 2000 times magnification;

[0065] Figure 22 Fig. 15 is a scanning electron microscope image of the boronized porous alloy rod of Example 1, wherein (a) is an electron microscope image at 200 times magnification and (b) is an electron microscope image at 2000 times magnification;

[0066] Figure 23 Electrochemical test curves of the porous iron-nickel alloy rod and the boronized porous alloy rod in Example 1;

[0067] Figure 24 Electrochemical test curves of the boronized porous alloy rod in Example 1 at 1000 mA cm -2 Stability test curves at large current density;

[0068] Figure 25 Electrochemical test curves of the ordinary boronized porous alloy rod and the boronized porous alloy rod corrected by electrochemically active specific surface area in Example 1. DETAILED DESCRIPTION

[0069] The application will be further described in detail below with specific examples.

[0070] The application discloses a compact high-efficiency hydrogen-oxygen generator electrolytic cell with adjustable gas production, which comprises a barrel 3, and the barrel 3 is sealed at both ends by an upper end cover 1 and a lower end cover 2.

[0071] A plurality of insulating partitions 9 are arranged in the barrel 3; the insulating partitions 9 are combined and radially expanded, so that the inside of the barrel 3 is divided into a plurality of independent sealed electrolysis chambers 91; the sealed electrolysis chambers 91 are six fan-shaped cavities.

[0072] When installed, the two end portions of the insulating partitions 9 are embedded into radially grooves 11 on the corresponding surfaces of the upper end cover 1 and the lower end cover 2, so that the independent sealed electrolysis chambers 91 are isolated. The upper end cover 1, the lower end cover 2 and the barrel 3 therebetween are pulled tight by a plurality of screw rods 10, so that the upper end cover 1, the lower end cover 2 and the barrel 3 are fixed and sealed.

[0073] The insulating partitions 9 can adopt an integral molding structure.

[0074] A water outlet 6 is arranged in the middle of the upper end cover 1; the water outlet 6 is in communication with the independent sealed electrolysis chambers 91 respectively;

[0075] A water inlet 7 is arranged in the middle of the lower end cover 2; the water inlet 7 is in communication with the independent sealed electrolysis chambers 91 respectively;

[0076] A pair of electrode groups 8 are arranged in each of the sealed electrolysis chambers 91;

[0077] The sealed electrolysis chambers 91 serve as electrolytic cells; when the electrolytic cells work, electrolyte flows into the sealed electrolysis chambers 91 through the water inlets 7, and hydrogen-oxygen mixed gas and electrolyte flow out through the water outlets 6.

[0078] The electrode groups 8 comprise one anode 4 and one cathode 5 (a corrosion-resistant stainless steel pipe can be used);

[0079] The cathode 5 is a cylindrical structure, and the anode 4 is a columnar structure; the anode 4 is sleeved in the cathode 5;

[0080] An electrically conductive plate 51 is arranged at the end of the cathode 5, and is fixed by a bolt and extends outside the upper end cover 1 or the lower end cover 2 as a negative electrode interface of the sealed electrolysis chamber 91; and one end of the anode 4 is a threaded rod structure, which extends outside the upper end cover 1 or the lower end cover 2 as a positive electrode interface of the sealed electrolysis chamber 91.

[0081] The negative electrode interfaces and the positive electrode interfaces distributed on the upper end cover 1 or the lower end cover 2 are arranged alternately, so that the positive electrode and the negative electrode can be connected in proximity.

[0082] The anode 4 is a boronized porous electrode rod, and the diameter is 8-11.5 mm.

[0083] The cathode 5 is a stainless steel pipe; the stainless steel pipe is an austenitic stainless steel rich in iron, chromium and nickel elements, the inner diameter is 12-14 mm, and the outer diameter is 14-16 mm.

[0084] The boronized porous electrode rod is prepared by a boronizing heat treatment process of boron-rare earth co-permeation on a porous iron-nickel alloy rod; the catalytic layer of boride on the surface of the porous electrode rod has high stability due to the catalytic permeation of the rare earth element, so that the porous electrode rod has long stability under harsh working conditions in actual electrolysis; meanwhile, the rare earth element can adjust the electronic structure of the metal boride catalytic layer, so as to improve the intrinsic catalytic activity and realize optimization of reaction thermodynamics and kinetics. The boronized porous electrode rod can improve the electrolysis efficiency and increase the maximum gas production under the premise of not increasing the use amount of electrode material and ensuring the stability of the electrolysis tank.

[0085] As shown in Figure 6 and Figure 7 , the anode 4 and the cathode 5 are labeled at the positive and negative electrode connection interfaces of the upper end cover 1 and the lower end cover 2; the anode boronized porous electrode rod is marked as 1+, 2+, 3+, 4+, 5+ and 6+ at the connection interfaces of the upper end cover 1 and the lower end cover 2; and the cathode 5 is marked as 1-, 2-, 3-, 4-, 5- and 6- at the connection interfaces of the upper end cover 1 and the lower end cover 2.

[0086] Based on the above structure design, the circuit connection of the six separate sealed electrolysis chambers 91 in the hydrogen-oxygen generator electrolysis tank has multiple modes; the circuit connection mode can be flexibly changed according to the gas production demand of the actual application scene, so as to achieve the purpose of adjusting the gas production.

[0087] The circuit connection mode one is that the circuits of the separate sealed electrolysis chambers 91 are connected in series, as shown in Figure 8 ; the six separate sealed electrolysis chambers 91 are divided into three groups, the circuits of two sealed electrolysis chambers 91 in each group are connected in series, and the circuits among the three groups are connected in parallel; the specific connection mode of each connection interface of the upper end cover 1 and the lower end cover 2 can be referred to the connection mode shown in the above embodiment.Figure 9 and Figure 10 .

[0088] The circuit connection mode two is shown in the figure, and the circuit connection of each separate sealed electrolytic chamber 91 is shown in the figure. Figure 11 The six separate sealed electrolytic chambers 91 are divided into two groups, the circuit of each group of three sealed electrolytic chambers 91 is connected in series, and the circuit between the two groups is connected in parallel. Figure 12 and Figure 13 .

[0089] The circuit connection mode three is shown in the figure. Figure 14 The circuit connection of each separate sealed electrolytic chamber 91 is shown in the figure. Figure 15 and Figure 16 .

[0090] The circuit connection mode four is shown in the figure. Figure 17 The six separate sealed electrolytic chambers 91 are divided into two groups, the circuit of each group of three sealed electrolytic chambers 91 is connected in series, and the circuit between the two groups is connected in parallel. Figure 18 and Figure 19 ;

[0091] The circuit connection mode of the six separate sealed electrolytic chambers 91 in the hydrogen-oxygen generator electrolytic cell of the application is not limited to the above four modes, and more series and parallel combinations of the circuit connection mode of the six separate sealed electrolytic chambers 91 can be made according to the actual application scene needs.

[0092] As described above, by optimizing the structure design of the electrolytic cell and replacing the high-efficiency electrode material, the production capacity can be adjusted and the maximum production capacity can be increased on the basis of retaining the compact structure design. The entire hydrogen-oxygen generator electrolytic cell system is not more than 0.8L, and 0.23-1.37 liters of mixed gas can be stably produced per minute, which meets the demand of most vehicle-mounted hydrogen production.

[0093] The boronized porous electrode rod preparation method of the application can be realized by the following steps:

[0094] Step one: weigh the boronizing agent, activator, filler and rare earth catalyst and mix them thoroughly to obtain a boronizing agent A;

[0095] Step two: embed the porous iron-nickel alloy rod into the boronizing agent A obtained in step one to obtain mixture B; the mass content of nickel element in the porous iron-nickel alloy rod is 30-50%, and the rest is iron element;

[0096] Step three: after calcination treatment of the mixture B obtained in step two, mixture C is obtained;

[0097] Step four: take out the porous iron-nickel alloy rod in the mixture C obtained in step three, and after washing and drying, a boronized porous electrode rod is obtained.

[0098] In step one, the mass ratio of the boron supply agent, the activator, the filler and the rare earth catalyst is (1-10):(1-6):(3-17):(0.2-4).

[0099] In step three, the calcination temperature of the calcination treatment is 580-1000℃, and the calcination time is 1-20 hours.

[0100] In step four, the washing refers to ultrasonic treatment with water and ethanol for 5-10 minutes respectively; and the drying refers to drying in a drying oven for 0.2-4 hours, and the drying temperature is 40-80℃.

[0101] The boron supply agent includes boron carbide, boron iron, borax and boric anhydride, etc.

[0102] The activator includes activated carbon, fluoroborate, carbonate and ammonium chloride, etc.

[0103] The filler includes silicon carbide and aluminum trioxide, etc.

[0104] The rare earth catalyst includes neodymium oxide, neodymium chloride, cerium oxide and cerium chloride, etc.

[0105] The preparation process of the boronized porous electrode rod is specifically described below through examples.

[0106] Example 1:

[0107] 1) Select boron carbide as the boron supply agent, activated carbon and potassium fluoroborate (mass ratio 1:16) as the activator, silicon carbide as the filler, and neodymium oxide as the rare earth catalyst; the above-mentioned boron supply agent, activator, filler and rare earth catalyst are weighed according to the mass ratio of 1:2:16:1 and mixed thoroughly to obtain boronizing agent A;

[0108] 2) Embed the porous iron-nickel alloy rod into the boronizing agent A obtained in step 1) to obtain mixture B; the mass content of nickel element in the porous iron-nickel alloy rod is 30-50%, and the rest is iron element;

[0109] 3) After calcination treatment of the mixture B obtained in step 2), mixture C is obtained; the calcination temperature is 900℃, and the calcination time is 6 hours.

[0110] 4) The porous iron-nickel alloy rod in mixture C obtained in step 3) is taken out, dried in a drying oven for 2 hours at 60°C after being ultrasonically cleaned with water and ethanol for 10 minutes respectively, to obtain a boronized porous alloy rod.

[0111] The porous iron-nickel alloy rod and the boronized porous alloy rod are subjected to X-ray diffraction test, and the results are shown in FIG. 2. The porous iron-nickel alloy rod of the present application is austenite phase of face-centered cubic structure; after the boronizing heat treatment of boron-rare earth co-permeation, the boronized porous alloy rod has strong B1Fe1Ni1 diffraction peak, indicating the generation of metal boride. Figure 20

[0112] The scanning electron microscope image of the porous iron-nickel alloy rod in Example 1 is shown in FIG. 3, and a three-dimensionally connected micro-nano pore structure is observed on the surface; Figure 21 The scanning electron microscope image of the boronized porous alloy rod in Example 1 is shown in FIG. 4, and it can be observed that the metal boride is generated in the original micro-nano structure pores. Further energy spectrum analysis is performed on the surface of the boronized porous alloy rod, and the results are shown in Table 1. In addition to iron, nickel and boron elements, the neodymium element is successfully detected, with a mass percentage of 1.56%, indicating that the neodymium element is successfully introduced into the metal boride on the surface of the boronized porous alloy. Figure 22 Table 1

[0113]

[0114] Element Class Atomic Number Characteristic X-ray Element Mass Percent Fe 26 K 64.14 Ni 28 K 28.83 B 5 K 5.47 Nd 60 L 1.56

[0115] In a three-electrode system, the porous iron-nickel alloy rod and the boronized porous alloy rod in the present example are used as the working electrode, a platinum sheet is used as the counter electrode, and mercury / mercury oxide is used as the reference electrode. Electrochemical test is performed in a Gamry electrochemical workstation to evaluate the catalytic activity. The test electrolyte is 1 mol / L potassium hydroxide aqueous solution. The test mode adopted is linear sweep voltammetry, the scanning speed is 5 mV / s, and the test voltage interval after conversion to the relative reversible hydrogen electrode potential is 1.2-1.6 V (vs. RHE).

[0116] The test results are shown in FIG. 5. The current density of the porous iron-nickel alloy rod reaches 10 mA cm-2, and the overpotential is as high as 310 mV. In comparison, after the boronizing heat treatment of boron-rare earth co-permeation, the catalytic activity of the boronized porous alloy rod is significantly improved. The current density reaches 10 mA cm-2, and the overpotential is 239 mV. The current density reaches 1000 mA cm-2, and the overpotential is only 343 mV. Figure 23 -2 -2 -2

[0117] ​​​​​The above results show that the reaction thermodynamics and kinetics conditions of the boronized porous alloy rod prepared by the present application are effectively improved, and the electrolysis efficiency can be greatly improved, so as to achieve the purpose of increasing the gas production.

[0118] At the same time, the long-term stability test of the boronized porous alloy rod is carried out at a large current density of 1000 mA cm -2 , and as shown in Figure 24 , the boronized porous alloy rod prepared by the present application can work for at least 200 hours under actual harsh working conditions, and the catalytic activity does not greatly decay, which is not possessed by the ordinary boronized porous alloy rod reported previously.

[0119] In order to better highlight the advantages of the boronized porous alloy rod prepared by the present application, an ordinary boronized porous alloy rod (without adding rare earth elements for the same boronizing heat treatment) is further prepared. After the electrochemical active specific surface area correction of the ordinary boronized porous alloy rod and the boronized porous alloy rod prepared by the present application, the electrochemical test is carried out, and the test results reflecting the intrinsic catalytic activity are shown in Figure 25 . The intrinsic catalytic activity of the boronized porous alloy rod prepared by the present application is far superior to that of the ordinary boronized porous alloy rod, and the corrected current density of the boronized porous alloy rod prepared by the present application reaches 10 mA cm -2 , and the overpotential is 290 mV, while the corrected current density of the ordinary boronized porous alloy rod reaches 10 mA cm -2 , and the overpotential is close to 400 mV.

[0120] As can be seen, thanks to the catalytic penetration of rare earth elements in the boronizing process and the modulation effect on the electronic structure of metal boride, the boronized porous electrode prepared by the boron-rare earth co-penetration boronizing heat treatment process in the present application has the advantages of good stability, high intrinsic catalytic activity, etc. Therefore, using the boronized porous electrode rod as an anode, the electrolysis efficiency can be greatly improved under the premise of ensuring the stability and compactness of the hydrogen-oxygen generator electrolytic tank, so as to achieve the purpose of increasing the gas production.

[0121] Example 2:

[0122] 1) Select boron iron as a boron supplier, activated carbon and sodium fluoroborate (mass ratio of 1:3) as an activator, aluminum oxide as a filler, and neodymium chloride as a rare earth catalytic penetrant; the above-mentioned boronizing agent, activator, filler and rare earth catalytic penetrant are weighed according to the mass ratio of 6:4:9:1, and are fully mixed to obtain a boronizing agent A;

[0123] 2) The porous iron-nickel alloy rod is embedded into the boronizing agent A obtained in step 1) to obtain a mixture B; the mass content of nickel element in the porous iron-nickel alloy rod is 30-50%, and the rest is iron element;

[0124] 3) The mixture B obtained in step 2) is subjected to calcination treatment, the calcination temperature is 700℃, and the calcination time is 15 hours, to obtain mixture C;

[0125] 4) The porous iron-nickel alloy rod in the mixture C obtained in step 3) is taken out, and after being ultrasonically treated with water and ethanol for 10 minutes respectively, it is placed into a drying box to be dried for 4 hours, the drying temperature is 50℃, to obtain a boronized porous alloy rod.

[0126] After the boron-rare earth co-permeation boronizing heat treatment, the surface of the prepared boronized porous alloy rod is subjected to energy spectrum analysis, and the results are shown in Table 2. In addition to iron, nickel and boron elements, neodymium element is successfully detected, with a mass percentage of 1.48%, indicating that the neodymium element is successfully introduced into the metal boride on the surface of the boronized porous alloy. The prepared boronized porous iron-based alloy rod has the advantages of good stability, high intrinsic catalytic activity, and the like. The corresponding test results are similar to those of Example 1.

[0127] Table 2

[0128] Element Class Atomic Number Characteristic X-ray Element Mass Percent Fe 26 K 65.01 Ni 28 K 27.65 B 5 K 5.86 Nd 60 L 1.48

[0129] Example 3:

[0130] 1) Borax is selected as a boron source, activated carbon and sodium fluoroborate (mass ratio of 1:2) are selected as activators, silicon carbide is selected as a filler, and cerium oxide is selected as a rare earth catalyst; the above-mentioned boronizing agent, activator, filler and rare earth catalyst are weighed according to the mass ratio of 10:3:6:1 and mixed thoroughly to obtain a boronizing agent A;

[0131] 2) The porous iron-nickel alloy rod is embedded into the boronizing agent A obtained in step 1) to obtain a mixture B; the mass content of nickel element in the porous iron-nickel alloy rod is 30-50%, and the rest is iron element;

[0132] 3) The mixture B obtained in step 2) is subjected to calcination treatment, the calcination temperature is 600℃, and the calcination time is 20 hours, to obtain mixture C;

[0133] 4) The porous iron-nickel alloy rod in the mixture C obtained in step 3) is taken out, and after being ultrasonically treated with water and ethanol for 10 minutes respectively, it is placed into a drying box to be dried for 4 hours, the drying temperature is 40℃, to obtain a boronized porous alloy rod.

[0134] After the boron-rare earth co-permeation boronizing heat treatment, the surface of the prepared boronized porous alloy rod is subjected to energy spectrum analysis, and the results are shown in Table 3. In addition to iron, nickel and boron elements, cerium element is successfully detected, with a mass percentage of 2.01%, indicating that the cerium element is successfully introduced into the metal boride on the surface of the boronized porous alloy. The prepared boronized porous iron-based alloy rod has the advantages of good stability, high intrinsic catalytic activity, and the like. The corresponding test results are similar to those of Example 1.

[0135] Table 3

[0136] Element Class Atomic Number Characteristic X-ray Element Mass Percent Fe 26 K 63.89 Ni 28 K 27.78 B 5 K 6.32 Ce 58 L 2.01

[0137] Example 4:

[0138] 1) Select boric anhydride as boron source, activated carbon and potassium fluoroborate (mass ratio of 1:1) as activator, aluminum oxide as filler, and cerium chloride as rare earth catalyst; the above-mentioned boron source, activator, filler and rare earth catalyst are weighed according to the mass ratio of 3:4:12:1 and mixed thoroughly to obtain boronizing agent A;

[0139] 2) The porous iron-nickel alloy rod is embedded into the boronizing agent A obtained in step 1) to obtain mixture B; the mass content of nickel element in the porous iron-nickel alloy rod is 30-50%, and the rest is iron element;

[0140] 3) The mixture B obtained in step 2) is calcined at a calcination temperature of 800℃ for 10 hours to obtain mixture C;

[0141] 4) The porous iron-nickel alloy rod in the mixture C obtained in step 3) is taken out, ultrasonic treated with water and ethanol for 10 minutes respectively, and then placed in a drying box for drying for 1 hour at a drying temperature of 80℃ to obtain boronized porous alloy rod.

[0142] After boron-rare earth co-permeation and boronizing heat treatment, the surface of the prepared boronized porous alloy rod is analyzed by energy spectrum, and the results are shown in Table 4. In addition to iron, nickel and boron elements, cerium element is successfully detected, with a mass percentage of 1.73%, indicating that cerium element is successfully introduced into the metal boride on the surface of the boronized porous alloy. The prepared boronized porous alloy rod has the advantages of good stability, high intrinsic catalytic activity, and the like. The corresponding test results are similar to those of Example 1.

[0143] Table 4

[0144] Element Class Atomic Number Characteristic X-ray Element Mass Percent Fe 26 K 64.08 Ni 28 K 28.14 B 5 K 6.05 Ce 58 L 1.73

[0145] As described above, the present application can be better implemented.

[0146] The embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations and simplifications made without departing from the spirit and principles of the present application shall be equivalent replacement modes and shall be included in the protection scope of the present application.

Claims

1. A compact high efficiency hydrogen-oxygen generator electrolyzer with adjustable gas production, characterized in that, It comprises a cylinder (3) whose both ends are sealed by an upper end cover (1) and a lower end cover (2); A plurality of insulating partitions (9) are arranged in the cylinder (3); these insulating partitions (9) are combined to be radially expanded, thereby separating the inside of the cylinder (3) into a plurality of separate sealed electrolysis chambers (91); A water outlet (6) is arranged in the middle of the upper end cover (1); the water outlet (6) is in communication with these separate sealed electrolysis chambers (91) respectively; A water inlet (7) is arranged in the middle of the lower end cover (2); the water inlet (7) is in communication with these separate sealed electrolysis chambers (91) respectively; A pair of electrode groups (8) are arranged in each of the sealed electrolysis chambers (91); The sealed electrolysis chamber (91) is used as an electrolytic cell; when the electrolytic cell works, electrolyte flows into these sealed electrolysis chambers (91) through the water inlet (7) and the generated hydrogen-oxygen mixed gas and electrolyte flow out through the water outlet (6); The electrode group (8) comprises an anode (4) and a cathode (5); The cathode (5) is in a cylindrical structure and the anode (4) is in a columnar structure; the anode (4) is sleeved in the cathode (5); An electrically conductive plate (51) is arranged at the end of the cathode (5) and is fixed by a bolt and extends outside the upper end cover (1) or the lower end cover (2) to serve as a negative electrode interface of the sealed electrolysis chamber (91); one end of the anode (4) is in a threaded rod structure which extends outside the upper end cover (1) or the lower end cover (2) to serve as a positive electrode interface of the sealed electrolysis chamber (91); The anode (4) is a boronized porous electrode rod; The preparation of the boronized porous electrode rod comprises the following steps: Step one: weigh the boronizing agent, activating agent, filler and rare earth catalyst and mix them thoroughly to obtain a boronizing agent A; Step two: embed the porous iron-nickel alloy rod into the boronizing agent A obtained in step one to obtain a mixture B; the mass content of nickel in the porous iron-nickel alloy rod is 30-50% and the rest is iron; Step three: perform calcination treatment on the mixture B obtained in step two to obtain a mixture C; Step four: take out the porous iron-nickel alloy rod in the mixture C obtained in step three, wash and dry it to obtain a boronized porous electrode rod; The negative electrode interfaces and the positive electrode interfaces distributed on the upper end cover (1) or the lower end cover (2) are arranged alternately, which facilitates the connection of the positive and negative electrodes; The circuit connection mode between a plurality of adjacent sealed electrolysis chambers (91) is changed to flexibly adjust the gas production.

2. The compact high efficient oxyhydrogen generator cell with adjustable gas production according to claim 1, characterized in that, The diameter of the boronized porous electrode rod is 8-11.5 mm.

3. The compact high efficient oxyhydrogen gas generator electrolyzer with adjustable gas production according to claim 1, characterized in that, The cathode (5) is a stainless steel pipe; the stainless steel pipe is an austenitic stainless steel rich in iron, chromium and nickel, has an inner diameter of 12-14 mm and an outer diameter of 14-16 mm.

4. The compact high efficient oxyhydrogen generator electrolyzer with adjustable gas production according to claim 1, characterized in that, In step one, the mass ratio of the boronizing agent, activating agent, filler and rare earth catalyst ranges from (1-10) : (1-6) : (3-17) : (0.2-4).

5. The compact high efficient oxyhydrogen gas generator electrolyzer with adjustable gas production according to claim 1, characterized in that, In step three, the calcination temperature of the calcination treatment is 580-1000℃ and the calcination time is 1-20 hours.

6. The compact high efficient oxyhydrogen gas generator cell with adjustable gas production according to claim 1, wherein, In step four, the washing refers to ultrasonic cleaning with water and ethanol for 5-10 minutes respectively. Drying refers to drying for 0.2 to 4 hours using a drying oven at a temperature of 40 to 80°C.

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