阅读说明：本技术 一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法 (Preparation method of low-cost titanium-based manganese dioxide composite anode for seawater electrolysis hydrogen production ) 是由 唐长斌 刘子龙 崔段段 俞永奇 李志港 于丽花 薛娟琴 于 2021-09-30 设计创作，主要内容包括：一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法,在钛基材表面电弧热喷涂制备出(Ti+Zr)N中间层,而后在其上阳极电沉积制备(Mn-(1-x)Mo-(x))O-(2+x)-WC活性层,获得Ti/(Ti+Zr)N/(Mn-(1-x)Mo-(x))O-(2+x)-WC形稳阳极。本发明利用(Ti+Zr)N取代IrO-(2)中间层,且选用纳米尺度的碳化钨对掺Mo的二氧化锰氧化物活性层进行复合协同,有效利用了中间层优异的导电性,以及耐酸、碱、盐的抗腐蚀性,并经电弧喷涂制备使得表面粗化,比表面积明显增多,有助于活性表层具有更多的活性位点；产品表面裂纹宽度显著缩小,活性层细化、致密,且厚度增大,在实际工况下的析氧效率电解可达到99.9％。(A low-cost Ti-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen is prepared through arc hot spraying to prepare the intermediate layer of (Ti + Zr) N on the surface of Ti substrate, and electrodeposition to prepare (Mn) 1‑x Mo x )O 2+x A WC active layer to obtain Ti/(Ti + Zr) N/(Mn) 1‑x Mo x )O 2+x -a WC dimensionally stable anode. The invention uses (Ti + Zr) N to replace IrO 2 The middle layer is formed by compounding and cooperating the Mo-doped manganese dioxide oxide active layer by using nano-scale tungsten carbide, so that the excellent conductivity of the middle layer and the corrosion resistance of acid, alkali and salt are effectively utilized, the surface is roughened by arc spraying, the specific surface area is obviously increased, and more active sites are provided for the active surface layer; the width of the crack on the surface of the product is obviously reduced, the active layer is refined and compact, the thickness is increased, and the oxygen evolution efficiency can reach 99.9% under the actual working condition.)

1. A preparation method of a low-cost titanium-based manganese dioxide composite anode for seawater electrolysis hydrogen production is characterized in that firstly, a (Ti + Zr) N intermediate layer is prepared on the surface of a pretreated titanium substrate by electric arc thermal spraying, then a WC composite manganese molybdenum oxide active surface layer is prepared on the upper surface of the (Ti + Zr) N intermediate layer by anode composite electrodeposition, and finally Ti/(Ti + Zr) N/(Mn) molybdenum oxide active surface layer is obtained_1-xMo_x)O_2+x-WC dimensionally stable coated anodes, wherein x is the number of moles and is 0.1-0.2.

2. The preparation method of the low-cost titanium-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen according to claim 1, wherein the pretreatment of the titanium substrate comprises alkali washing for removing oil, oxalic acid etching and sand blasting, so that an uneven rough surface layer is formed on the surface, the rough surface layer is gray, the metallic luster is lost, and a clean surface without oil stains and oxide scales is obtained.

3. The preparation method of the low-cost titanium-based manganese dioxide composite anode for hydrogen production by seawater electrolysis as claimed in claim 1, wherein the arc thermal spraying adopts a two-wire co-feeding mode, the selected spraying wires, one is a pure zirconium wire and the other is a pure titanium wire, the spraying wires penetrate through the center of a spraying nozzle in an atmospheric environment, the spraying power is set to be 30-40kW, the arc voltage is 5-35V, the spraying distance is 100-250mm, the compressed air pressure is 0.3-1.0MPa, and a (Ti + Zr) N middle layer is formed by the reaction of the spraying wires with nitrogen and oxygen in the air by means of high-temperature high-speed flame flow in the spraying process.

4. The preparation method of the low-cost titanium-based manganese dioxide composite anode for the seawater electrolysis hydrogen production according to claim 3, characterized in that the pretreated titanium substrate is preheated by electric arc spraying before the intermediate layer is prepared, and the temperature is controlled to be 70-150 ℃.

5. The method for preparing the low-cost titanium-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen according to claim 1, 3 or 4, wherein the thickness of the (Ti + Zr) N intermediate layer is 30-200 μm.

6. The method for preparing the low-cost titanium-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen according to claim 1, wherein the composite electrodeposition preparation of the WC composite manganese molybdenum oxide active surface layer is carried out by taking Ti/(Ti + Zr) N as an anode and two stainless steel plates with equal area as a cathode and placing the stainless steel plates in a reactor containing MnSO₄、Na₂MoO₄Nano-sized WC fine particles and H₂SO₄The mixed solution of (3) is subjected to electrodeposition preparation.

7. The method for preparing the low-cost titanium-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen according to claim 1, wherein MnSO is contained in the mixed solution₄Na with a concentration of 0.2-0.3mol/L₂MoO₄The concentration is 0.02-0.04mol/L, the addition amount of nano WC particles is 5-30g/L, and H is used₂SO₄Adjusting the pH of the solution to 0.5 and the electrodeposition temperature to 70-9The electrodeposition time is 20-60min at 0 ℃, and the current density is 400-^-2。

8. The preparation method of the low-cost titanium-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen according to claim 6 or 7, characterized in that after the deposition is finished, the prepared anode is washed clean by distilled water and dried by hot air, and the Ti/(Ti + Zr) N/(Mn) with compact and uniform surface is obtained_1-xMo_x)O_2+x-a WC dimensionally stable anode material.

9. The method for preparing the low-cost titanium-based manganese dioxide composite anode for the hydrogen production by electrolyzing seawater according to claim 6, wherein before the anode and the cathode are placed in a mixed solution, the anode is degreased and cleaned, and is subjected to 10-20% HNO₃Etching in the solution for 2-3 min.

10. The method for preparing the low-cost titanium-based manganese dioxide composite anode for the hydrogen production by seawater electrolysis as claimed in claim 6, wherein the mechanical stirring is kept on the mixed solution during the electrodeposition preparation process to ensure the suspension of WC particles, and the stirring rate is controlled at 200-600 rpm.

Technical Field

The invention belongs to the technical field of preparation of electrocatalytic dimensionally stable anode materials, and particularly relates to a preparation method of a low-cost titanium-based manganese dioxide composite anode for seawater electrolysis hydrogen production.

Background

The hydrogen energy has the advantages of high combustion heat value, abundant sources, convenient transportation and storage and green and pollution-free reaction products, and is considered as the most potential energy carrier in the future and the best substitute of the traditional fossil energy. The hydrogen production by electrolyzing water has the advantages of high hydrogen production purity and the like, and is expected to be great, the extra cost of water purification and the like is avoided by adopting seawater electrolysis, and the hydrogen can be produced by directly utilizing the widely-existing seawater or brackish water, so the seawater hydrogen electrolysis energy development is preferentially considered. However, the production of hydrogen by seawater electrolysis requires that the anode cannot release toxic chlorine and must have the characteristics of high efficiency and long service life of oxygen evolution reaction.

However, a great deal of research has demonstrated that almost all available anode materials preferentially produce chlorine gas during the electrolysis of seawater, and it is known that only manganese oxides preferentially produce oxygen gas in the seawater electrolysis anode reaction, and although its oxygen evolution efficiency is not sufficient to avoid chlorine evolution, titanium-based MnO is not sufficient₂The coating anode still becomes in the seawater environmentThe most promising anode materials.

In order to better achieve engineering application, the titanium substrate and MnO are usually selected at present₂A layer of noble metal oxide (IrO) is added between the coatings₂Best performance) intermediate layer to block active oxygen attack and thereby prevent the formation of insulating TiO on the titanium substrate surface₂The film utilizes the characteristics of excellent conductivity, stability and the like. However, the noble metal oxide has various problems of rare reserves, high price and the like besides complicated preparation process (hot brush coating and repeated brush coating and pyrolysis), thereby greatly limiting the application of the noble metal oxide in practical engineering. In addition, for the surface layer MnO₂In order to enhance the conductivity and the oxygen evolution and chlorine inhibition catalytic activity of the active layer, the active layer is usually doped with Mo, W, Fe, V and other elements to enhance the oxygen evolution efficiency and avoid the generation of chlorine, but the element doping causes MnO₂The effectiveness of the enhancement of conductivity and activity of the coating is still limited.

Disclosure of Invention

Aiming at overcoming the IrO existing in the preparation technology of the titanium-based manganese dioxide coating electrode for electrolyzing seawater to prepare hydrogen₂The intermediate layer has high cost and complex preparation process, and the defects that the conductivity and the catalytic activity of the coating can not be obviously changed only by element doping are overcome, the invention aims to provide the preparation method of the low-cost titanium-based manganese dioxide composite anode for electrolyzing seawater to prepare hydrogen, and the conductive (Ti + Zr) N intermediate layer is sprayed by electric arc under atmospheric atmosphere to replace noble metal oxide IrO₂The preparation technology of the pyrolysis layer and the electric arc spraying is simple and convenient to operate, easy to control, rapid in coating, high in working efficiency and remarkably reduced in preparation cost; and in view of that since a small amount of Mo or the like is doped to MnO₂The oxygen evolution efficiency can be improved in the coating, considering that the catalytic activity of W is close to that of Mn and has higher catalytic activity than that of Mo, WC with characteristics such as Pt-like (tungsten carbide WC has a hexagonal crystal structure and an electronic surface structure similar to that of noble metal platinum, shows good catalytic performance for oxygen reaction, has excellent high hardness and is corrosion-resistant) is selected for compounding, and the remarkable improvement of the oxygen evolution catalytic activity and the oxygen evolution efficiency is realized by cooperating with Mo doping. The invention is realized by spraying TiN on a titanium substrate by electric arcThe interlayer and the surface are subjected to electrodeposition to prepare a WC composite Mo-doped manganese dioxide coating, and finally Ti/(Ti + Zr) N/(Mn) is obtained_1-xMo_x)O_2+x-a WC anode. The dimensionally stable anode has high oxygen evolution efficiency, good chlorine inhibition characteristic and good electrode durability.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of a low-cost titanium-based manganese dioxide composite anode for hydrogen production by seawater electrolysis comprises the steps of firstly preparing a (Ti + Zr) N intermediate layer with good conductivity and corrosion resistance on the surface of a pretreated titanium substrate by arc thermal spraying, then preparing a WC composite manganese molybdenum oxide active surface layer on the upper surface of the (Ti + Zr) N intermediate layer by anode composite electrodeposition, and finally obtaining Ti/(Ti + Zr) N/(Mn) with high oxygen evolution efficiency and long service life_1-xMo_x)O_2+x-WC dimensionally stable coated anodes, wherein x is the number of moles and is 0.1-0.2.

Further, the pretreatment of the titanium substrate comprises alkali washing oil removal, oxalic acid etching and sand blasting treatment, so that an uneven rough surface layer is formed on the surface, the rough surface layer is gray and loses metal luster, and a clean surface without oil stains and oxide scales is obtained.

Further, the arc thermal spraying uses a two-wire co-feed mode, one of the selected spraying wire materials is a pure zirconium wire, the other is a pure titanium wire, the spraying wire material penetrates through the center of the spraying nozzle in the atmospheric environment, and the tip of the metal wire is continuously heated to the melting point in annular flame formed around the nozzle and the gas hood. Then, the particles are atomized by compressed air passing through the air hood to form spray particles, the spray particles are sprayed onto the substrate by means of air flow acceleration, so that the molten particles are cooled to a plastic or semi-molten state, and the molten particles are rapidly reacted with nitrogen and oxygen in the air in the atomization process to form nitrogen/oxide of metal zirconium and titanium, and the nitrogen/oxide is cladded and deposited on the surface of the pretreated titanium substrate.

Further, the spraying power is 30-40kW, the arc voltage is 5-35V, the spraying distance is 100-250mm, the pressure of compressed air is 0.3-1.0MPa, and the spraying time is 10-30s, wherein a (Ti + Zr) N middle layer which has good conductivity, acid resistance, alkali resistance and salt resistance and is tightly combined with the titanium substrate is formed by reacting the spraying wire with nitrogen and oxygen in the air by means of high-temperature high-speed flame flow in the spraying process.

Furthermore, the diameter of the pure zirconium wire and the pure titanium wire is 1.5-2.5 mm.

Further, the thickness of the (Ti + Zr) N intermediate layer is 30-200 μm.

Further, before preparing the intermediate layer for good bonding, the pretreated titanium substrate is preheated by arc spraying, and the temperature is controlled to be 70-150 ℃.

In the process of preparing the (Ti + Zr) N middle layer by electric arc spraying, if the spraying distance is too long, the temperature and the speed of ions reaching the matrix are too low, particles are not deposited, and the oxidation degree of the particles is improved; too short a residence time of the particles in the flame stream is too short to heat and accelerate sufficiently, and therefore a distance of 10-20cm is generally chosen.

Furthermore, the composite electrodeposition preparation of the WC composite manganese-molybdenum oxide active surface layer takes Ti/(Ti + Zr) N as an anode and two stainless steel plates with equal area as a cathode and is placed in a reactor containing MnSO₄、Na₂MoO₄Nano-sized WC fine particles and H₂SO₄The mixed solution of (3) is subjected to electrodeposition preparation. Then the prepared anode is washed clean by distilled water and dried by hot air, and the Ti/(Ti + Zr) N/(Mn-Mo) O with compact and uniform surface and good stability and activity is obtained_x-a WC dimensionally stable anode material.

Further, MnSO is contained in the mixed solution₄Na with a concentration of 0.2-0.3mol/L₂MoO₄The concentration is 0.02-0.04mol/L, the addition amount of nano WC particles is 5-30g/L, and H is used₂SO₄Adjusting the pH value of the solution to 0.5, the electro-deposition temperature to 70-90 ℃, the electro-deposition time to 20-60min, and the current density to 400-^-2。

Further, before the anode and the cathode are placed in the mixed solution, the anode is degreased and cleaned and is subjected to 10-20% HNO₃Etching in the solution for 2-3 min.

Further, the mixed solution is kept mechanically stirred during the preparation process of the electrodeposition to ensure that WC particles are suspended, and the stirring speed is controlled at 200-600 rpm.

Compared with the currently accepted Ti/IrO for electrolyzing seawater to prepare hydrogen₂/(Mn_1-xMo_x)O_2+xCompared with the anode preparation technology, the invention prepares the (Ti + Zr) N intermediate layer on the titanium substrate by using the electric arc spraying technology, and then prepares Ti/(Ti + Zr) N/(Mn) by using the anode deposition technology_1-xMo_x)O_2+x-a WC anode. The invention uses (Ti + Zr) N to replace noble metal oxide IrO₂The middle layer is a nano-scale tungsten carbide active layer (Mn) doped with Mo_1-xMo_x)O_2+x) The composite cooperation is carried out, the excellent conductivity of the (Ti + Zr) N middle layer and the corrosion resistance of acid, alkali and salt are effectively utilized, the surface is coarsened through the electric arc spraying preparation, the specific surface area is obviously increased, and the active surface layer is facilitated to have more active sites. The preparation of the (Ti + Zr) N interlayer by electric arc spraying greatly simplifies the preparation of IrO by a brushing method₂The intermediate layer is complicated, the cost of noble metal Ir, Ru oxide and the like serving as intermediates is effectively reduced, and the electric arc spraying process is convenient to operate, two wires are simultaneously fed in the electric arc spraying process, so that the spraying efficiency is high, the operation cost is low, and the cost is low. Meanwhile, the combination of the nano WC composite technology and element doping is introduced into the preparation of the titanium-based manganese dioxide modified anode, so that the problems of low catalytic activity, poor stability and the like of the anode can be obviously solved. WC compounded Ti/TiN/(Mn)_1-xMo_x)O_2+xThe width of the surface crack of the anode is obviously reduced, the active layer is thinned and compact, and the thickness is increased, so that Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+xThe oxygen evolution efficiency of the-WC anode under the actual working condition can reach 99.9 percent, and the electrolysis is reduced after 200 hours of use, thereby showing good substitution application prospect.

Drawings

FIG. 1 is a schematic of the arc sprayed (Ti + Zr) N interlayer preparation of the present invention.

FIG. 2 is a schematic representation of the structure of a (Ti + Zr) N interlayer prepared in accordance with the present invention.

FIG. 3 is a scanning electron microscope image of the surface of the (Ti + Zr) N intermediate layer prepared by the present invention.

FIG. 4 is a scanning electron micrograph of a cross section of a (Ti + Zr) N interlayer prepared according to the present invention.

FIG. 5 is an X-ray diffraction pattern of the (Ti + Zr) N interlayer prepared by the present invention.

FIG. 6 is an X-ray diffraction pattern of the surface layer of the anode prepared by the method of the present invention.

FIG. 7 is a comparison of the evolution of the oxygen evolution efficiency over time of anodes prepared by the process of the invention when electrolyzed at 90 ℃ in 3.5 wt% NaCl solution at pH 12.

Detailed Description

The embodiments of the present invention will be described in detail below with reference to the drawings and examples.

Example 1

Firstly, a titanium plate which is subjected to polishing, alkali washing and acid washing is used as a substrate, then an electric arc spraying technology is adopted to prepare a (Ti + Zr) N middle layer, finally, a Ti/(Ti + Zr) N electrode material is used as an anode, stainless steel with equal area size is used as a cathode, and the anode is subjected to electrooxidation to prepare (Mn)_1-xMo_x)O_2+xA WC active layer, thereby obtaining Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+x-a WC electrode.

Preparation of the (Ti + Zr) N intermediate layer as shown in fig. 1, the spray wires were pure zirconium wire and pure titanium wire, respectively, in a two-wire co-feed manner, the spray wires were passed through the center of the spray nozzle in an atmospheric environment, and the tips of the metal wires were continuously heated to their melting points in an annular flame formed around the nozzle and the gas shield. Then, the particles are atomized by compressed air passing through the air hood to form spray particles, the spray particles are sprayed onto the substrate by means of air flow acceleration, so that the molten particles are cooled to a plastic or semi-molten state, and the molten particles are rapidly reacted with nitrogen and oxygen in the air in the atomization process to form nitrogen/oxide of metal zirconium and titanium, and the nitrogen/oxide is cladded and deposited on the surface of the pretreated titanium substrate.

The preparation process parameters of the (Ti + Zr) N interlayer in the embodiment are as follows: diameter of titanium and zirconium wire: 1.8 mm; the preheating temperature is 80 ℃; the spraying power is 36 kW; the working voltage is 30V; the spraying distance is 10 cm.

(Mn_1-xMo_x)O_2+xThe WC active layer anodic electrodeposition conditions are as follows: the formula of the deposition solution is 0.2mol/L MnSO₄、0.03/L Na₂MoO₄·2H₂O and 10g/L nano-scale WC with a current density of 600 A.m^-2Depositing at 80 deg.C for 30min, electromagnetically stirring, and treating with H₂SO₄The solution pH was adjusted to 0.5. The prepared Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+xAnd (4) washing the WC electrode by using distilled water, and drying by using cold air to obtain the dimensionally stable anode with a compact and uniform surface. The electrode structure is observed, compared with the titanium matrix surface, the Ti/(Ti + Zr) N matrix of the (Ti + Zr) N middle layer sprayed by the electric arc has larger roughness and correspondingly more specific surface area, and the prepared active layer has more active sites.

Ti/(Ti+Zr)N/(Mn_1-xMo_x)O_2+x-WC anode compared to Ti/TiN/(Mn) without WC recombination_1-xMo_x)O_2+xThe anode, the surface crack width is significantly reduced, the active layer is uniform and dense, and the thickness is increased, as shown in fig. 2, 3 and 4.

XRD analysis of the surface of the (Ti + Zr) N intermediate layer revealed that the prepared (Ti + Zr) N intermediate layer was a multi-phase composition having TiN and ZrN as main phases, and the higher melting point zirconium had a higher oxygen affinity than titanium, and therefore, the intermediate layer composition exhibited a higher amount of mixed phases of zirconium oxide, as shown in FIG. 5.

For Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+xAnd Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+xXRD analysis of the WC anode surface, as shown in FIG. 6, shows that the coatings obtained are all in the form of γ -MnO₂Is a coating of the major phase (JCPDS No.30-0820), which is consistent with the general crystallographic characteristics of electrodeposited manganese dioxide. When the coating is compounded by introducing nano-scale tungsten carbide (JCPDS No.20-1316) particles, the coating is influenced by WC diffraction peak, MnO₂Diffraction peaks (2 θ 37.120, 42.401, 56.027, 75.022, and 78.921) are characterized by a shift to the right to some extent. Meanwhile, the peak apparently belonging to WC diffraction was also shown at an angle of 62.027 ° 2 θ.

Example 2

The long-term durability of the electrode is improved by using 1000 A.m^-2Is evaluated by continuous electrolysis in a 3.5 wt.% NaCl solution at 90 ℃ and pH 12And (6) estimating. In actual seawater electrolysis, the anode and cathode compartments would be separated to avoid mixing of hydrogen and oxygen. Due to H⁺And OH^-The pH of the anolyte rapidly decreases and the pH of the catholyte rapidly increases. If H is allowed⁺And OH^-The ions mix and combine to produce water molecules, which neutralize the acidity or alkalinity of the electrolyte. Therefore, in the actual electrolysis process, alkaline catholyte is periodically introduced into the anode chamber, electrolyzed in the anode chamber to the pH value of about 7, and then returned to the catholyte tank. Therefore, a 3.5 wt% NaCl solution having a pH of 12 was used to check the durability of the electrode. Pure titanium (C)>99.98%) was used as counter electrode in the electrolysis process. The oxygen evolution efficiency is determined by measuring 1000 A.m in 300ml of 3.5 wt.% NaCl solution^-2Until 300 coulombs of charge are passed. The content of oxygen released was estimated by the difference between the total charge consumed by electrolysis and the charge of chlorine formed during electrolysis, and the amounts of chlorine and hypochlorite generated in the electrolyte were determined by iodometry (GB 19106) -2003.

Under the actual working condition, the Ti/(Ti + Zr) N/(Mn) of the invention_1-xMo_x)O_2+x-WC and Ti/(Ti + Zr) N/(Mn)_{1- x}Mo_x)O_2+xElectrode and Ti/IrO for electrolyzing seawater₂/(Mn_1-xMo_x)O_2+xComparative tests were carried out on the oxygen evolving anodes, and referring to FIG. 7, it can be seen from comparative tests of the evolution efficiency of the electrolysis of oxygen with time of the three electrodes that the intermediate layer of (Ti + Zr) N, which is arc sprayed, is Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+x-WC and Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+xThe anode is connected with Ti/IrO containing noble metal oxide interlayer in the initial stage of electrolysis₂/(Mn-Mo)O_xThe oxygen evolution efficiency of the anode is close to 100%. Wherein the surface layer is compounded with Ti/(Ti + Zr) N/(Mn) of tungsten carbide_1-xMo_x)O_2+xThe WC anode shows the most excellent performance, the oxygen evolution efficiency in the initial stage of electrolysis can reach 99.9%, and the performance of the electrode begins to be remarkably reduced after 200 hours of electrolysis, which is shown as the remarkable reduction of the oxygen evolution performance. And Ti/(Ti + Zr) N/(Mn) of undoped WC_1-xMo_x)O_2+xAnd Ti/IrO₂/(Mn_1-xMo_x)O_2+xThe oxygen evolution performance of the anode is continuously degraded within 100 hours of electrolysis, wherein the Ti/(Ti + Zr) N/(Mn)_1-xMo_x)O_2+xThe oxygen evolution performance of the anode is only 15.9% in 100h, and the Ti/(Ti + Zr) N/(Mn) prepared by the method is shown to be_1-xMo_x)O_2+xThe WC electrode has good application effect in actual working conditions, and the intermediate layer prepared by electric arc spraying can achieve the same effect as the noble metal oxide intermediate layer in a short time.

The method for preparing the low-cost titanium-based manganese dioxide composite anode for hydrogen production by seawater electrolysis is described in detail, and the specific examples are used for explaining the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention; for those skilled in the art, the invention can be modified in the specific embodiments and applications according to the spirit of the present invention, and therefore the content of the present description should not be construed as limiting the invention.