CN118345410A - A titanium alloy bipolar plate with high pitting potential and low resistivity and a method for preparing the same - Google Patents
A titanium alloy bipolar plate with high pitting potential and low resistivity and a method for preparing the same Download PDFInfo
- Publication number
- CN118345410A CN118345410A CN202410570418.XA CN202410570418A CN118345410A CN 118345410 A CN118345410 A CN 118345410A CN 202410570418 A CN202410570418 A CN 202410570418A CN 118345410 A CN118345410 A CN 118345410A
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- bipolar plate
- rolling
- percent
- alloy bipolar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/046—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种高点蚀电位和低电阻率钛合金双极板及其制备方法，按质量百分含量计，所述钛合金双极板的组成包含：Mo：3.0％～5.0％，Ni：0.1％～0.3％，Ru：0.005％～0.05％，余量为Ti，杂质元素(Fe、O、C、N、H)总含量不超过0.01％；本发明的钛合金双极板在满足导电性要求基础上，能够提高所述钛合金双极板的点蚀电位，从而从根本上解决钛合金双极板在电解水制氢电解槽的服役环境中，由于点蚀电位较低导致其耐蚀性相对较差、产氢效率低的问题。The invention discloses a titanium alloy bipolar plate with high pitting potential and low resistivity and a preparation method thereof. The composition of the titanium alloy bipolar plate comprises, by mass percentage, 3.0% to 5.0% Mo, 0.1% to 0.3% Ni, 0.005% to 0.05% Ru, the remainder being Ti, and the total content of impurity elements (Fe, O, C, N, H) not exceeding 0.01%. The titanium alloy bipolar plate of the invention can improve the pitting potential of the titanium alloy bipolar plate on the basis of meeting the conductivity requirement, thereby fundamentally solving the problem that the titanium alloy bipolar plate has relatively poor corrosion resistance and low hydrogen production efficiency due to low pitting potential in the service environment of a water electrolysis hydrogen production electrolyzer.
Description
Technical Field
The invention relates to the technical field of water electrolysis hydrogen production, in particular to a titanium alloy bipolar plate with high pitting corrosion potential and low resistivity and a preparation method thereof.
Background
The hydrogen energy is used as clean energy with great development potential in the 21 st century, has the characteristics of abundant reserves, zero pollution, dense energy, wide application and the like, and the utilization of the hydrogen energy is gradually valued by countries around the world. At present, the electrolytic water hydrogen production has the characteristics of environmental protection, flexible production, high purity (generally more than 99.7 percent), high-value oxygen byproduct and the like, and becomes a main source of green hydrogen.
The electrolytic water hydrogen production is basically divided into proton exchange membrane electrolytic water hydrogen Production (PEM), alkaline anion exchange membrane electrolytic water hydrogen production (AEM), alkaline electrolytic water hydrogen production (ALK) and high temperature solid oxide electrolytic water hydrogen production (SOEC) according to the difference of the diaphragm materials of the electrolytic cell. The PEM water electrolysis hydrogen production device has the advantages of compact structure, high current density, high response speed and small occupied area, and can operate at a lower temperature (20-80 ℃). The highly dynamic PEM water electrolysis hydrogen production technology is very suitable for converting electric energy into hydrogen energy for high-efficiency storage based on wave energy generated by renewable energy sources such as wind energy, solar energy and the like, and realizes no carbonization of global energy in the future.
Bipolar plates are a critical component in PEM electrolyzed water hydrogen plants. The proton exchange membrane and catalyst support device is connected with each single cell in the PEM electrolytic stack, and is used for carrying water, oxygen, hydrogen, electrons and other substances and heat transfer through the flow channels of the proton exchange membrane and catalyst support device, the manufacturing cost of the proton exchange membrane and catalyst support device is about half of the total cost of the electrolytic stack, and the proton exchange membrane and catalyst support device plays a decisive role in the service performance and service life of the PEM electrolytic stack. Titanium alloys have significant advantages as bipolar plates with excellent corrosion resistance, high strength, high thermal conductivity, low permeability and low resistivity. However, the corrosion resistance of the titanium alloy bipolar plate is relatively poor and the hydrogen production efficiency is low due to the low pitting potential in the service environment of the PEM electrolytic water hydrogen production electrolytic tank, namely the sulfuric acid solution environment containing F — ions, so that the corrosion resistance of the bipolar plate needs to be further improved by improving the pitting potential of the bipolar plate in the high-potential service environment facing the anode of the PEM electrolytic water tank, the power of the electrolytic water tank is improved, and the hydrogen production efficiency is increased.
Disclosure of Invention
In view of the above, the present disclosure provides a titanium alloy bipolar plate with high pitting corrosion potential and low resistivity and a preparation method thereof, which solves the problems of relatively poor corrosion resistance and low hydrogen production efficiency of the titanium alloy bipolar plate due to low pitting corrosion potential in the service environment of an electrolytic water electrolysis hydrogen production electrolytic tank.
To achieve the above object, according to a first aspect, the high pitting corrosion potential and low resistivity titanium alloy bipolar plate comprises the following components in percentage by mass:
Mo:3.0 to 5.0 percent of Ni:0.1 to 0.3 percent of Ru:0.005% -0.08%, the balance being Ti, the total content of impurity elements (Fe, O, C, N, H) is not more than 0.1%.
In this disclosure and possible embodiments, the composition is:
Mo:3.0 to 5.0 percent of Ni:0.1 to 0.3 percent of Ru:0.008 to 0.05 percent, the balance being Ti, and the total content of impurity elements (Fe, O, C, N, H) is not more than 0.01 percent.
In this disclosure and possible embodiments, the composition is:
Mo:3.5 to 5.0 percent of Ni:0.1 to 0.2 percent, ru:0.01 to 0.03 percent, the balance being Ti, and the total content of impurity elements (Fe, O, C, N, H) is not more than 0.1 percent.
In a second aspect, the preparation method of the Gao Dianshi-potential and low-resistivity titanium alloy bipolar plate according to the first aspect includes the steps of proportioning, smelting, rolling and annealing heat treatment, in which:
The raw materials of the ingredients are selected from titanium sponge, titanium foil, electrolytic nickel powder, electrolytic ruthenium powder and molybdenum particles.
In the disclosed and possible embodiments, the smelting process employs vacuum arc smelting with a vacuum arc smelting current of 300A-400A; the times of vacuum arc melting are 4-6 times, and each melting time is 1-2 min.
In the disclosed and possible embodiments, argon is introduced as a protective atmosphere and an ionized gas during the vacuum arc melting, and the vacuum degree of the vacuum arc furnace chamber is below 5×10 -3 Pa.
In the disclosed and possible embodiments, the rolling procedure is to perform homogenization treatment on the Ti-Mo-Ni-Ru titanium alloy cast ingot obtained after vacuum arc melting, and then obtain a Ti-Mo-Ni-Ru titanium alloy slab through rolling deformation;
The homogenization treatment is carried out at 700-800 ℃ for 8-12 h.
In the disclosed and possible embodiments, the total deformation amount of the rolling deformation is 75% -85%;
The rolling deformation adopts multi-pass rolling, the deformation of each pass is 35-45%, the rolling temperature of each pass is 900-920 ℃, and the heat preservation is carried out for 2-3 min between each pass of rolling.
In the disclosed and possible embodiments, after the homogenization treatment, the Ti-Mo-Ni-Ru titanium alloy ingot is placed in a heating furnace, and after heat preservation is performed at 910 ℃ for 40min, the rolling deformation is performed.
In the disclosed and possible embodiments, the annealing heat treatment procedure is to place the Ti-Mo-Ni-Ru titanium alloy slab in a heating furnace, control the annealing temperature to be 700-800 ℃, keep the temperature for 50-70 min, and then air cool to room temperature.
The invention has the following beneficial effects:
According to the preparation method of the high-pitting potential and low-resistivity titanium alloy bipolar plate, specific alloy components and contents are selected, and then corresponding technological parameters are optimally designed in smelting, rolling and annealing heat treatment procedures, so that the high-pitting potential and low-resistivity titanium alloy bipolar plate can be finally obtained, the purpose of improving the pitting potential of the titanium alloy bipolar plate can be achieved on the basis of meeting the conductivity requirement of the bipolar plate, and the problems that the corrosion resistance of the titanium alloy bipolar plate is relatively poor and the hydrogen production efficiency is low due to low pitting potential in the service environment of a water electrolysis hydrogen production electrolytic tank are effectively solved.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent from the following description of embodiments thereof with reference to the accompanying drawings in which:
FIG. 1 is a Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy ingot of example 1 of this disclosure;
FIG. 2 is a Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy rolled annealed sheet material of example 1 of the present disclosure;
FIG. 3 is a Tafel plot of rolled annealed Ti-3.0Mo-0.2Ni-0.01Ru, pure titanium, and TA10 plates of example 1 of the present disclosure in a 0.5M sulfuric acid +5 ppmF-solution environment;
FIG. 4 is a Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy ingot of example 2 of the disclosure;
FIG. 5 is a Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy rolled annealed sheet of example 2 of the present disclosure;
FIG. 6 is a Tafel plot of a rolled annealed Ti-3.5Mo-0.2Ni-0.01Ru sheet according to example 2 of the present disclosure in a 0.5M sulfuric acid +5 ppmF-solution environment;
FIG. 7 is a Ti-4Mo-0.2Ni-0.01Ru titanium alloy ingot of example 3 of this disclosure;
FIG. 8 is a Ti-4Mo-0.2Ni-0.01Ru titanium alloy rolled annealed sheet material of example 3 of the present disclosure;
FIG. 9 is a Tafel plot of a rolled annealed Ti-4Mo-0.2Ni-0.01Ru slab of example 3 of the present disclosure in a 0.5M sulfuric acid +5 ppmF-solution environment;
FIG. 10 is a Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy ingot of example 4 of this disclosure;
FIG. 11 is a Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy rolled annealed sheet material of example 4 of the present disclosure;
FIG. 12 is a Tafel plot of a rolled annealed Ti-3.5Mo-0.2Ni-0.04Ru sheet in 0.5M sulfuric acid +5 ppmF-solution environment of example 4 of the present disclosure;
FIG. 13 is a Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy ingot of example 5 of this disclosure;
FIG. 14 is a Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy rolled annealed sheet material of example 5 of the present disclosure;
FIG. 15 is a Tafel plot of a rolled annealed Ti-3.5Mo-0.1Ni-0.01Ru sheet according to example 5 of the present disclosure in a 0.5M sulfuric acid +5 ppmF-solution environment.
Detailed Description
The present disclosure is described below based on embodiments, but it is worth noting that the present disclosure is not limited to these embodiments. In the following detailed description of the present disclosure, certain specific details are set forth in detail. However, for portions not described in detail, those skilled in the art can also fully understand the present disclosure. Meanwhile, unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, it is the meaning of "including but not limited to".
The high pitting potential and low resistivity titanium alloy bipolar plate and the preparation method thereof are described in detail through specific embodiments, wherein in each specific embodiment, the titanium alloy bipolar plate comprises the following chemical components in percentage by mass: mo:3.0 to 5.0 percent, ni:0.1 to 0.3 percent, ru:0.01 to 0.03 percent, the balance being Ti, and the total content of impurity elements (Fe, O, C, N, H) is not more than 0.01 percent.
The design principle of the titanium alloy bipolar plate adopting the chemical components is as follows: since Mo element has the effect of improving the pitting potential of pure Ti, and Ni and Ru elements have the effect of reducing the pitting potential of pure Ti, the resistivity of pure Ti can be effectively improved. Therefore, the invention selects a large amount of Mo element, a small amount of Ni and Ru element to add pure Ti.
In each specific embodiment, the preparation method of the titanium alloy bipolar plate comprises the following steps:
(1) And (3) batching:
selecting titanium alloy raw materials for smelting according to the chemical components of the bipolar plate, and then weighing and proportioning the selected raw materials; the raw materials used in the specific embodiments are selected from titanium sponge, titanium foil, electrolytic nickel powder, electrolytic ruthenium powder and molybdenum particles. Wherein, the titanium foil is used for coating electrolytic nickel powder and electrolytic ruthenium powder, and prevents the electrolytic nickel powder and the electrolytic ruthenium powder from being blown away by an electric arc in the smelting process.
(2) Smelting:
smelting the raw materials after the proportioning to obtain Ti-Mo-Ni-Ru titanium alloy ingots; the smelting is performed by adopting vacuum arc smelting, wherein the vacuum arc smelting current is 300-400A, the vacuum arc smelting times are 4-6 times, each time of smelting is 1-2 min, and the Ti-Mo-Ni-Ru titanium alloy cast ingot is obtained after the vacuum arc smelting.
Because the affinity of titanium and oxygen is higher, the invention selects vacuum arc melting, can effectively avoid excessive oxygen from being melted into titanium alloy, and can conveniently and repeatedly melt for a plurality of times, and has better component uniformity.
(3) Rolling:
Homogenizing the Ti-Mo-Ni-Ru titanium alloy cast ingot obtained after vacuum arc melting, and then rolling and deforming to obtain a Ti-Mo-Ni-Ru titanium alloy slab. In each specific embodiment, in order to uniformly distribute beta stabilizing elements Mo, ni and Ru and not excessively grow crystal grains, the homogenization treatment is performed at a temperature of 700-800 ℃ for 8-12 hours.
The total deformation amount of the rolling deformation is 75-85%; in each specific embodiment, the rolling deformation adopts multi-pass rolling, the deformation of each pass is 35-45%, the rolling temperature of each pass is 900-920 ℃, and the heat preservation is carried out for 2-3 min between each pass of rolling. The invention adopts multi-pass rolling deformation based on the consideration of full penetration of thermal deformation, and the control of single-pass deformation is based on the purpose of grain refinement.
(4) Annealing heat treatment:
Placing the Ti-Mo-Ni-Ru titanium alloy plate blank obtained in the step (3) into a heating furnace for heat preservation and then air-cooling to obtain a titanium alloy bipolar plate substrate of a corresponding embodiment; in each specific embodiment, the annealing temperature is 700-800 ℃, the heat preservation time is 50-70 min, and then the air cooling is carried out to room temperature.
In the invention, the annealing heat treatment is to eliminate the residual stress of the hot rolled slab and to eliminate the thermal deformation texture, wherein the design of the annealing temperature and the annealing time takes the completion of recrystallization into consideration, and particularly, the principle that the growth of recrystallized grains does not occur is adopted.
The following examples are only some of the preferred embodiments and do not limit the scope and technical means of the foregoing invention in any way.
Example 1
(1) And (3) batching:
the alloy is prepared according to the nominal composition Ti-3.0Mo-0.2Ni-0.01Ru (mass percent), titanium particles (purity is more than or equal to 99.99 wt%), high-purity titanium foil (thickness is 0.03mm, purity is 99.99 wt%), electrolytic nickel powder (purity is 99.99 wt%), electrolytic ruthenium powder (purity is 99.99 wt%) and molybdenum particles (purity is 99.99 wt%), and the alloy is weighed according to the total weight of 25 g.
(2) Smelting:
Cleaning the inner wall of a copper crucible of a non-consumable vacuum arc furnace in advance, and then placing the prepared smelting raw materials into the copper crucible, and coating electrolytic nickel powder and electrolytic ruthenium powder with titanium foil. The furnace chamber is evacuated to a vacuum degree of 5X 10 -3 Pa, and then high-purity argon is introduced as protective atmosphere and ionized gas, and the vacuum degree is about 0.05MPa. The current is controlled to be not more than 400A, magnetic stirring is carried out, the smelting time is about 1min each time, then the ingot is turned over to be smelted again, and the like, smelting is repeated for 5 times to ensure that the components of the ingot are uniform, and then the copper mold is used for suction casting to obtain the Ti-3.0Mo-0.2Ni-0.01Ru ingot, and the concrete is shown in figure 1.
(3) Rolling:
Placing the Ti-3.0Mo-0.2Ni-0.01Ru titanium alloy cast ingot into a heating furnace for homogenization treatment, preserving heat for 12h at 800 ℃, and then cooling to room temperature. Before rolling, the cast ingot is placed in a heating furnace, heat preservation is carried out for 40min at 910 ℃, and then rolling deformation is carried out on a two-roller hot rolling mill. And adopting a multi-pass rolling deformation process, wherein the total rolling reduction is 80%, the pass rolling reduction is 40%, and returning the hot rolled blank to the furnace between each pass, and preserving heat for 2min at 910 ℃ to ensure the rolling temperature. And air cooling after rolling is finished, and finally obtaining the Ti-3.0Mo-0.2Ni-0.01Ru titanium alloy hot rolled plate.
(4) Annealing heat treatment:
and (3) placing the Ti-3.0Mo-0.2Ni-0.01Ru titanium alloy hot rolled plate into a heating furnace for annealing heat treatment, wherein the heat treatment process is 750 ℃ for 60min. Subsequently, the annealed sheet was air-cooled to room temperature, and finally a Ti-3.0Mo-0.2Ni-0.01Ru titanium alloy sheet was obtained, as shown in FIG. 2.
(5) Performance test:
According to the standard of GB/T40299-2021, a Ti-3.0Mo-0.2Ni-0.01Ru titanium alloy plate is cut into a corrosion resistance test sample, then the sample is ground and polished, an electrochemical workstation is adopted for testing immediately after polishing, and a polished surface is tested under the condition of 0.5M sulfuric acid +5 ppmF-solution at room temperature to obtain a Tafel curve shown in figure 3, wherein the pitting potential is 2.3V and is higher than the pitting potential (2V) of pure titanium and the pitting potential (1.8V) of a typical brand titanium alloy TA 10.
The bulk phase resistivity of the Ti-3.0Mo-0.2Ni-0.01Ru titanium alloy is 0.63 mu omega-m, is close to the resistivity of pure titanium (0.6-0.7 mu omega-m), is smaller than the resistivity of TC4 alloy (1.6-1.8 mu omega-m), has excellent conductivity, and can meet the conductivity requirement of a bipolar plate.
Example 2
(1) And (3) batching:
The alloy composition Ti-3.5Mo-0.2Ni-0.01Ru (mass percent) is prepared, titanium particles (purity is more than or equal to 99.99 wt%), high-purity titanium foil (thickness is 0.03mm, purity is 99.99 wt%), electrolytic nickel powder (purity is 99.99 wt%), electrolytic ruthenium powder (purity is 99.99 wt%) and molybdenum particles (purity is 99.99 wt%), and the alloy composition is weighed according to the total weight of 25 g.
(2) Smelting:
Placing the prepared smelting raw materials into a water-cooled copper crucible of a non-consumable vacuum arc furnace, wherein electrolytic nickel powder and electrolytic ruthenium powder are coated by titanium foil, and cleaning the inner wall of the copper crucible in advance. The vacuum degree of the furnace chamber of the vacuum arc furnace is pumped to below 5 multiplied by 10 - 3 Pa, then high-purity argon is introduced as protective atmosphere and ionized gas, and the vacuum degree is about 0.05MPa. The current is controlled to be not more than 400A, magnetic stirring is carried out, the smelting time is about 1min each time, then the ingot is turned over to be smelted again, and the like, smelting is repeated for 5 times to ensure that the components of the ingot are uniform, and then the copper mold is used for suction casting to obtain the Ti-3.5Mo-0.2Ni-0.01Ru ingot, and the concrete is shown in figure 4.
(3) Rolling:
Placing the Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy cast ingot into a heating furnace for homogenization treatment, preserving heat for 12h at 800 ℃, and then cooling to room temperature. Before rolling, the cast ingot is placed in a heating furnace, heat preservation is carried out for 40min at 910 ℃, and then rolling deformation is carried out on a two-roller hot rolling mill. And adopting a multi-pass rolling deformation process, wherein the total rolling reduction is 80%, the pass rolling reduction is 40%, and returning the hot rolled blank to the furnace between each pass, and preserving heat for 2min at 910 ℃ to ensure the rolling temperature. And air cooling after rolling is finished, and finally obtaining the Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy hot rolled plate.
(4) Annealing heat treatment:
And (3) placing the Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy hot rolled plate into a heating furnace for annealing heat treatment, wherein the heat treatment process is 750 ℃ for 60min. Subsequently, the annealed sheet was air-cooled to room temperature, and finally a Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy sheet was obtained, as shown in FIG. 5.
(5) Performance test:
Cutting a Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy plate into a corrosion resistance test sample, grinding and polishing the sample, immediately testing by an electrochemical workstation after polishing, and testing the polished surface under the condition of 0.5M sulfuric acid +5ppmF & lt- & gt solution at room temperature to obtain a Tafel curve shown in figure 6, wherein the pitting potential is 2.4V and higher than that of pure titanium and a typical brand titanium alloy TA 10.
The bulk phase resistivity of the Ti-3.5Mo-0.2Ni-0.01Ru titanium alloy is 0.65 mu omega-m, is close to the resistivity of pure titanium (0.6-0.7 mu omega-m), is smaller than the resistivity of the Ti-6Al-4V alloy (1.6-1.8 mu omega-m), has excellent conductivity, and can meet the conductivity requirement of the bipolar plate.
Example 3
(1) And (3) batching:
The alloy composition Ti-4Mo-0.2Ni-0.01Ru (mass percent) is prepared, titanium particles (purity is more than or equal to 99.99 wt%), high-purity titanium foil (thickness is 0.03mm, purity is 99.99 wt%), electrolytic nickel powder (purity is 99.99 wt%), electrolytic ruthenium powder (purity is 99.99 wt%) and molybdenum particles (purity is 99.99 wt%), and the alloy composition is weighed according to the total weight of 25 g.
(2) Smelting:
Placing the prepared smelting raw materials into a water-cooled copper crucible of a non-consumable vacuum arc furnace, wherein electrolytic nickel powder and electrolytic ruthenium powder are coated by titanium foil, and cleaning the inner wall of the copper crucible in advance. The vacuum degree of the furnace chamber of the vacuum arc furnace is pumped to below 5 multiplied by 10 - 3 Pa, then high-purity argon is introduced as protective atmosphere and ionized gas, and the vacuum degree is about 0.05MPa. The current is controlled to be not more than 400A, magnetic stirring is carried out, the smelting time is about 1min each time, then the ingot is turned over to be smelted again, and the like, smelting is repeated for 5 times to ensure that the components of the ingot are uniform, and then the copper mold is used for suction casting to obtain the Ti-4Mo-0.2Ni-0.01Ru ingot, and the concrete is shown in figure 7.
(3) Rolling:
Placing the Ti-4Mo-0.2Ni-0.01Ru titanium alloy cast ingot into a heating furnace for homogenization treatment, preserving heat for 12h at 800 ℃, and then cooling to room temperature in air.
Before rolling, the cast ingot is placed in a heating furnace, heat preservation is carried out for 40min at 910 ℃, and then rolling deformation is carried out on a two-roller hot rolling mill. And adopting a multi-pass rolling deformation process, wherein the total rolling reduction is 80%, the pass rolling reduction is 40%, and returning the hot rolled blank to the furnace between each pass, and preserving heat for 2min at 910 ℃ to ensure the rolling temperature. And (3) air cooling after rolling is finished, and finally obtaining the Ti-4Mo-0.2Ni-0.01Ru titanium alloy hot rolled plate.
(4) Annealing heat treatment:
And (3) placing the Ti-4Mo-0.2Ni-0.01Ru titanium alloy hot rolled plate into a heating furnace for annealing heat treatment, wherein the heat treatment process is 750 ℃ for 60min. Subsequently, the annealed sheet was air-cooled to room temperature, and finally a Ti-4Mo-0.2Ni-0.01Ru titanium alloy sheet was obtained, as shown in FIG. 8.
(5) Performance test:
Cutting a Ti-4Mo-0.2Ni-0.01Ru titanium alloy plate into a corrosion resistance test sample, grinding and polishing the sample, immediately testing by an electrochemical workstation after polishing, and testing a polished surface under the condition of 0.5M sulfuric acid +5ppmF & lt- & gt solution at room temperature to obtain a Tafel curve shown in figure 9, wherein the pitting potential is 2.4V and higher than that of pure titanium and a typical brand titanium alloy TA 10.
The bulk resistivity of the Ti-4Mo-0.2Ni-0.01Ru titanium alloy is 0.6 mu omega-m, is close to the resistivity of pure titanium (0.6-0.7 mu omega-m), is smaller than the resistivity of the Ti-6Al-4V alloy (1.6-1.8 mu omega-m), has excellent conductivity, and can meet the conductivity requirement of the bipolar plate.
Example 4
(1) And (3) batching:
The alloy composition Ti-3.5Mo-0.2Ni-0.04Ru (mass percent) is prepared, titanium particles (purity is more than or equal to 99.99 wt%), high-purity titanium foil (thickness is 0.03mm, purity is 99.99 wt%), electrolytic nickel powder (purity is 99.99 wt%), electrolytic ruthenium powder (purity is 99.99 wt%) and molybdenum particles (purity is 99.99 wt%), and the alloy composition is weighed according to the total weight of 25 g.
(2) Smelting:
Placing the prepared smelting raw materials into a water-cooled copper crucible of a non-consumable vacuum arc furnace, wherein electrolytic nickel powder and electrolytic ruthenium powder are coated by titanium foil, and cleaning the inner wall of the copper crucible in advance. The vacuum degree of the furnace chamber of the vacuum arc furnace is pumped to below 5 multiplied by 10 - 3 Pa, then high-purity argon is introduced as protective atmosphere and ionized gas, and the vacuum degree is about 0.05MPa. The current is controlled to be not more than 400A, magnetic stirring is carried out, the smelting time is about 1min each time, then the ingot is turned over to be smelted again, and the like, smelting is repeated for 5 times to ensure the components of the ingot to be uniform, and then the copper mold is used for suction casting to obtain the Ti-3.5Mo-0.2Ni-0.04Ru ingot, and the concrete is shown in figure 10.
(3) Rolling:
Placing the Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy cast ingot into a heating furnace for homogenization treatment, preserving heat for 12h at 800 ℃, and then cooling to room temperature. Before rolling, the cast ingot is placed in a heating furnace, heat preservation is carried out for 40min at 910 ℃, and then rolling deformation is carried out on a two-roller hot rolling mill. And adopting a multi-pass rolling deformation process, wherein the total rolling reduction is 80%, the pass rolling reduction is 40%, and returning the hot rolled blank to the furnace between each pass, and preserving heat for 2min at 910 ℃ to ensure the rolling temperature. And air cooling after rolling is finished, and finally obtaining the Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy hot rolled plate.
(4) Annealing heat treatment:
And (3) placing the Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy hot rolled plate into a heating furnace for annealing heat treatment, wherein the heat treatment process is 750 ℃ for 60min. Subsequently, the annealed sheet was air-cooled to room temperature, and finally a Ti-3.5Mo-0.2Ni-0.04Ruu titanium alloy sheet was obtained, as shown in FIG. 11.
(5) Performance test:
Cutting a Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy plate into a corrosion resistance test sample, grinding and polishing the sample, immediately testing by an electrochemical workstation after polishing, and testing the polished surface under the condition of 0.5M sulfuric acid +5ppmF & lt- & gt solution at room temperature to obtain a Tafel curve shown in figure 12, wherein the pitting potential is 2.4V and higher than that of pure titanium and a typical brand titanium alloy TA 10.
The bulk phase resistivity of the Ti-3.5Mo-0.2Ni-0.04Ru titanium alloy is 0.55 mu omega-m, is close to the resistivity of pure titanium (0.6-0.7 mu omega-m), is smaller than the resistivity of the Ti-6Al-4V alloy (1.6-1.8 mu omega-m), has excellent conductivity, and can meet the conductivity requirement of the bipolar plate.
Example 5
(1) And (3) batching:
The alloy composition Ti-3.5Mo-0.1Ni-0.01Ru (mass percent) is prepared, titanium particles (purity is more than or equal to 99.99 wt%), high-purity titanium foil (thickness is 0.03mm, purity is 99.99 wt%), electrolytic nickel powder (purity is 99.99 wt%), electrolytic ruthenium powder (purity is 99.99 wt%) and molybdenum particles (purity is 99.99 wt%), and the alloy composition is weighed according to the total weight of 25 g.
(2) Smelting:
Placing the prepared smelting raw materials into a water-cooled copper crucible of a non-consumable vacuum arc furnace, wherein electrolytic nickel powder and electrolytic ruthenium powder are coated by titanium foil, and cleaning the inner wall of the copper crucible in advance. The vacuum degree of the furnace chamber of the vacuum arc furnace is pumped to below 5 multiplied by 10 - 3 Pa, then high-purity argon is introduced as protective atmosphere and ionized gas, and the vacuum degree is about 0.05MPa. The current is controlled to be not more than 400A, magnetic stirring is carried out, the smelting time is about 1min each time, then the ingot is turned over to be smelted again, and the like, smelting is repeated for 5 times to ensure the components of the ingot to be uniform, and then the copper mold is used for suction casting to obtain the Ti-3.5Mo-0.1Ni-0.01Ru ingot, and the concrete is shown in figure 13.
(3) Rolling:
Placing the Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy cast ingot into a heating furnace for homogenization treatment, preserving heat for 12h at 800 ℃, and then cooling to room temperature. Before rolling, the cast ingot is placed in a heating furnace, heat preservation is carried out for 40min at 910 ℃, and then rolling deformation is carried out on a two-roller hot rolling mill. And adopting a multi-pass rolling deformation process, wherein the total rolling reduction is 80%, the pass rolling reduction is 40%, and returning the hot rolled blank to the furnace between each pass, and preserving heat for 2min at 910 ℃ to ensure the rolling temperature. And air cooling after rolling is finished, and finally obtaining the Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy hot rolled plate.
(4) Annealing heat treatment:
And (3) placing the Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy hot rolled plate into a heating furnace for annealing heat treatment, wherein the heat treatment process is 750 ℃ for 60min. Subsequently, the annealed sheet was air-cooled to room temperature, and finally a Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy sheet was obtained, as shown in FIG. 14.
(5) Performance test:
Cutting a Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy plate into a corrosion resistance test sample, grinding and polishing the sample, immediately testing by an electrochemical workstation after polishing, and testing the polished surface under the condition of 0.5M sulfuric acid +5ppmF & lt- & gt solution at room temperature to obtain a Tafel curve shown in figure 15, wherein the pitting potential is 2.4V and higher than that of pure titanium and a typical brand titanium alloy TA 10. .
The bulk phase resistivity of the Ti-3.5Mo-0.1Ni-0.01Ru titanium alloy is 0.63 mu omega-m, is close to the resistivity of pure titanium (0.6-0.7 mu omega-m), is smaller than the resistivity of the Ti-6Al-4V alloy (1.6-1.8 mu omega-m), has excellent conductivity, and can meet the conductivity requirement of the bipolar plate.
The above examples are merely representative of embodiments of the present disclosure, which are described in more detail and are not to be construed as limiting the scope of the present disclosure. It should be noted that modifications, equivalent substitutions, improvements, etc. can be made by those skilled in the art without departing from the spirit of the present disclosure, which are all within the scope of the present disclosure. Accordingly, the scope of protection of the present disclosure should be determined by the following claims.
Claims (10)
1. A high pitting potential and low resistivity titanium alloy bipolar plate, characterized in that the composition comprises, in mass percent:
mo:3.0 to 5.0 percent of Ni:0.1 to 0.3 percent of Ru:0.005% -0.05%, the balance being Ti, the total content of impurity elements (Fe, O, C, N, H) not exceeding 0.1%.
2. The titanium alloy bipolar plate of claim 1, wherein the composition is:
Mo:3.0 to 5.0 percent of Ni:0.1 to 0.3 percent of Ru:0.008 to 0.03 percent, the balance being Ti, and the total content of impurity elements (Fe, O, C, N, H) is not more than 0.01 percent.
3. The titanium alloy bipolar plate of claim 2, wherein the composition is:
Mo:3.5 to 5.0 percent of Ni:0.1 to 0.2 percent, ru:0.01 to 0.03 percent, the balance being Ti, and the total content of impurity elements (Fe, O, C, N, H) is not more than 0.01 percent.
4. A method for preparing a Gao Dianshi potential and low-resistivity titanium alloy bipolar plate as claimed in any one of claims 1-3, comprising the steps of proportioning, smelting, rolling and annealing heat treatment, and is characterized in that:
The raw materials of the ingredients are selected from titanium sponge, titanium foil, electrolytic nickel powder, electrolytic ruthenium powder and molybdenum particles.
5. The method for preparing the titanium alloy bipolar plate according to claim 4, wherein:
the smelting process adopts vacuum arc smelting, and the vacuum arc smelting current is 300A-400A; the times of vacuum arc melting are 4-6 times, and each melting time is 1-2 min.
6. The method for manufacturing a titanium alloy bipolar plate according to claim 4 or 5, wherein:
During the vacuum arc melting, argon is introduced as protective atmosphere and ionization gas, and the vacuum degree of the vacuum arc furnace chamber is below 5X 10 -3 Pa.
7. The method for preparing a titanium alloy bipolar plate according to claim 6, wherein:
The rolling procedure is that a Ti-Mo-Ni-Ru titanium alloy cast ingot obtained after vacuum arc melting is subjected to homogenization treatment, and then a Ti-Mo-Ni-Ru titanium alloy slab is obtained through rolling deformation;
The homogenization treatment is carried out at 700-800 ℃ for 8-12 h.
8. The method for preparing a titanium alloy bipolar plate according to claim 7, wherein:
The total deformation amount of the rolling deformation is 75% -85%;
The rolling deformation adopts multi-pass rolling, the deformation of each pass is 35-45%, the rolling temperature of each pass is 900-920 ℃, and the heat preservation is carried out for 2-3 min between each pass of rolling.
9. The method for preparing a titanium alloy bipolar plate according to claim 8, wherein:
after the homogenization treatment, placing the Ti-Mo-Ni-Ru titanium alloy cast ingot into a heating furnace, and carrying out rolling deformation after heat preservation for 40min at 910 ℃.
10. The method for producing a titanium alloy bipolar plate according to any one of claims 7 to 9, wherein:
The annealing heat treatment procedure is to place the Ti-Mo-Ni-Ru titanium alloy plate blank in a heating furnace, control the annealing temperature to be 700-800 ℃ and keep the temperature for 50-70 min, and then air-cool to room temperature.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410570418.XA CN118345410A (en) | 2024-05-09 | 2024-05-09 | A titanium alloy bipolar plate with high pitting potential and low resistivity and a method for preparing the same |
| PCT/CN2024/100082 WO2025231966A1 (en) | 2024-05-09 | 2024-06-19 | Titanium alloy bipolar plate with high pitting potential and low resistivity and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410570418.XA CN118345410A (en) | 2024-05-09 | 2024-05-09 | A titanium alloy bipolar plate with high pitting potential and low resistivity and a method for preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118345410A true CN118345410A (en) | 2024-07-16 |
Family
ID=91822531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410570418.XA Pending CN118345410A (en) | 2024-05-09 | 2024-05-09 | A titanium alloy bipolar plate with high pitting potential and low resistivity and a method for preparing the same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN118345410A (en) |
| WO (1) | WO2025231966A1 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666666A (en) * | 1984-11-22 | 1987-05-19 | Nippon Mining Co., Ltd. | Corrosion-resistant titanium-base alloy |
| JPH0689423B2 (en) * | 1985-11-05 | 1994-11-09 | 住友金属工業株式会社 | Titanium alloy with excellent corrosion resistance |
| JPS62109955A (en) * | 1985-11-08 | 1987-05-21 | Nippon Mining Co Ltd | Manufacture of titanium-base alloy material excellent in corrosion resistance |
| JPH02175850A (en) * | 1988-12-27 | 1990-07-09 | Nippon Mining Co Ltd | Production of corrosion resistant titanium alloy |
| JP4065146B2 (en) * | 2002-06-21 | 2008-03-19 | 新日本製鐵株式会社 | Titanium alloy having excellent corrosion resistance and method for producing the same |
| EP2889386B1 (en) * | 2013-01-25 | 2018-04-11 | Nippon Steel & Sumitomo Metal Corporation | Titanium alloy having excellent corrosion resistance in environment containing bromine ions |
| TW201910528A (en) * | 2017-08-07 | 2019-03-16 | 日商新日鐵住金股份有限公司 | Titanium block, manufacturing method thereof, and flat titanium blank for manufacturing titanium blocks at low cost |
| US11352687B2 (en) * | 2018-12-09 | 2022-06-07 | Titanium Metals Corporation | Titanium alloys having improved corrosion resistance, strength, ductility, and toughness |
| CN113462999B (en) * | 2020-03-30 | 2023-01-24 | 国核宝钛锆业股份公司 | Method for manufacturing titanium foil for bipolar plate |
-
2024
- 2024-05-09 CN CN202410570418.XA patent/CN118345410A/en active Pending
- 2024-06-19 WO PCT/CN2024/100082 patent/WO2025231966A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2025231966A1 (en) | 2025-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113789464B (en) | Ceramic phase reinforced refractory high-entropy alloy and preparation method thereof | |
| CN106319463B (en) | A kind of preparation method of rolling processing tungsten-titanium alloy target material | |
| CN109321766B (en) | Aluminum-air battery anode material and preparation method thereof | |
| CN108172807A (en) | A kind of single-phase A of multielement5B19Type superlattice hydrogen storage alloy electrode material and preparation method thereof | |
| CN110484788A (en) | Aluminium-air cell anode material and preparation method thereof and aluminium-air cell | |
| CN108179325A (en) | A kind of microalloying of rare earth aluminum alloy anode material and its preparation method and application | |
| CN112322934B (en) | Titanium alloy for bipolar plate of proton exchange membrane fuel cell | |
| CN115740003A (en) | Hydrogen fuel cell bipolar plate base material and preparation method of foil thereof | |
| CN111455248A (en) | A kind of magnesium air battery anode material and preparation method thereof | |
| CN108682867A (en) | A kind of magnesium-air cell anode band and its preparation method and application | |
| CN111187948A (en) | A lithium-aluminum alloy anode material with controllable phase composition, preparation method and application | |
| CN114657439A (en) | Refractory high-entropy alloy with good room-temperature plasticity and preparation method thereof | |
| CN114737036B (en) | A method for preparing high-plasticity titanium alloy ultra-thin plates for hydrogen fuel cell bipolar plates | |
| TW202026435A (en) | Sputtering target material | |
| CN112941356B (en) | Cu-MoNbTaVW refractory high-entropy alloy bicontinuous structural material and preparation method thereof | |
| CN111893365A (en) | Carbon-containing FeMnNiAlCr high-entropy alloy and preparation method thereof | |
| CN116397128A (en) | Rare earth copper chromium alloy material and preparation method thereof | |
| CN118345410A (en) | A titanium alloy bipolar plate with high pitting potential and low resistivity and a method for preparing the same | |
| CN105714169A (en) | Mo-Si-B-Hf-Al alloy bar and preparation method thereof | |
| CN118422241A (en) | Titanium bipolar plate for proton exchange membrane water electrolysis to produce hydrogen and preparation method thereof | |
| CN109355546B (en) | A kind of multi-principal alloy for making target material and preparation method thereof | |
| CN119092740A (en) | A corrosion-resistant titanium alloy bipolar plate and a preparation method thereof | |
| CN118086948A (en) | Porous high entropy alloy catalytic electrode based on B2-BCC structure, preparation method thereof and application in acidic oxygen evolution | |
| CN115976365B (en) | A titanium alloy for fuel cell bipolar plate and its preparation method and application | |
| CN103647063B (en) | Hydrogen storage electrode alloy for Ni-MH secondary battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |