CN114737036A - Preparation method of high-plasticity titanium alloy ultrathin plate for hydrogen fuel cell bipolar plate - Google Patents

Preparation method of high-plasticity titanium alloy ultrathin plate for hydrogen fuel cell bipolar plate Download PDF

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CN114737036A
CN114737036A CN202210324771.0A CN202210324771A CN114737036A CN 114737036 A CN114737036 A CN 114737036A CN 202210324771 A CN202210324771 A CN 202210324771A CN 114737036 A CN114737036 A CN 114737036A
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titanium alloy
plate
hydrogen fuel
fuel cell
ultrathin
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CN114737036B (en
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孔凡涛
朱海峰
王晓鹏
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a preparation method of a high-plasticity titanium alloy ultrathin plate for a hydrogen fuel cell bipolar plate, relates to the field of hydrogen fuel cells, and aims to solve the problem that a titanium alloy ultrathin plate special for the hydrogen fuel cell bipolar plate is lacked at present. The invention adopts high-purity nickel, high-purity niobium and high-purity zirconium as alloying elements to prepare titanium alloy, and the ultrathin sheet is prepared by smelting, high-temperature cogging, cold rolling and annealing. The preparation of the special titanium alloy ultrathin sheet can be realized by continuously using the existing industrial preparation equipment of the titanium alloy, and no additional special equipment is added, so that the large-scale industrial production can be realized, and the special titanium alloy ultrathin sheet has important commercial value. The invention is applied to the field of hydrogen fuel cells.

Description

Preparation method of high-plasticity titanium alloy ultrathin plate for hydrogen fuel cell bipolar plate
Technical Field
The invention relates to the field of hydrogen fuel cells, in particular to a preparation method of a high-plasticity titanium alloy ultrathin plate for a hydrogen fuel cell bipolar plate.
Background
The hydrogen fuel cell is a power generation device which directly converts chemical energy of hydrogen and oxygen into electric energy, only generates water, is environment-friendly, and is one of important development directions in the field of new energy automobiles at home and abroad. The bipolar plate of the hydrogen fuel cell for the new energy automobile is mainly manufactured by adopting a process of stamping and forming a metal ultrathin plate, accounts for about 20-30% of the total cost of the hydrogen fuel cell, has the volume and weight of about 70%, plays a role in supporting a membrane electrode, isolating reaction gas and guiding flow, and is one of core components of the hydrogen fuel cell. The ultrathin plate material for manufacturing the metal bipolar plate needs to have good corrosion resistance and electrical conductivity to meet the service life requirement of the hydrogen fuel cell, and the ultrathin plate material also needs to have excellent room temperature plasticity to meet the process requirement of stamping and forming the bipolar plate, which is also a necessary condition for the commercialization application of the ultrathin plate material in the field of the hydrogen fuel cell.
At present, the metal bipolar plate for the hydrogen fuel cell at home and abroad is mainly manufactured by 316L stainless steel ultrathin plates with the thickness of 0.05-0.15mm, the 316L stainless steel ultrathin plates have excellent room temperature plasticity and can meet the process requirement of stamping and forming the bipolar plate, but the 316L stainless steel has low corrosion resistance in the acid solution environment of the hydrogen fuel cell, the service life of the bipolar plate is seriously influenced, the hydrogen fuel cell can be scrapped when the corrosion resistance exceeds the corrosion resistance limit, and the development of an electric automobile with the hydrogen fuel cell is also limited. The titanium alloy is adopted as the bipolar plate of the hydrogen fuel cell, the corrosion resistance is obviously higher than that of stainless steel, so that the service life of the bipolar plate of the hydrogen fuel cell is obviously prolonged, and the density is reduced by more than 40% compared with the stainless steel, so that the weight specific power of the cell is obviously reduced, and the requirements of the whole automobile on the service life and weight reduction of the hydrogen fuel cell can be better met.
However, the existing titanium alloy in the industrial field is not designed according to the components of the hydrogen fuel cell working environment, and the corrosion resistance still cannot meet the requirement of long service life of the hydrogen fuel cell in the sulfuric acid solution environment containing F ions; meanwhile, because the existing titanium alloy has poor processability, the room temperature elongation is difficult to exceed 30 percent, and the lower room temperature plasticity is not beneficial to the cold rolling of ultrathin plates with the thickness of 0.05-0.15mm, and can not meet the requirement of the stamping forming of bipolar plates with fine groove structures, the titanium alloy is difficult to apply in the field of hydrogen fuel cells. Therefore, it is urgently needed to develop a high-plasticity titanium alloy special for bipolar plates and a corresponding ultrathin plate preparation technology with the thickness of 0.05-0.15mm so as to meet the requirement of hydrogen fuel cells on the titanium alloy.
Disclosure of Invention
The invention aims to solve the problem that a special titanium alloy ultrathin plate for a hydrogen fuel cell bipolar plate is lacked at present, and provides a preparation method of a high-plasticity titanium alloy ultrathin plate for the hydrogen fuel cell bipolar plate.
The invention relates to a preparation method of a high-plasticity titanium alloy ultrathin plate for a bipolar plate of a hydrogen fuel cell, which comprises the following steps of:
1) titanium alloy batching: accurately weighing the components according to the element proportion, and uniformly mixing the components, wherein the components of the titanium alloy are 0.05-1.0 wt.% of nickel element, 0.05-1.5 wt.% of niobium element, 0.05-1.5 wt.% of zirconium element, and the balance of titanium element and inevitable impurities;
2) preparing a titanium alloy ingot: carrying out fusion casting by adopting a vacuum non-consumable electrode arc melting furnace, or carrying out fusion casting by adopting a vacuum induction skull melting furnace, or carrying out fusion casting by adopting an electron beam cold hearth furnace, or carrying out two times of fusion casting by adopting the vacuum induction skull melting furnace and the vacuum consumable electrode arc melting furnace to prepare a titanium alloy ingot with uniform components;
3) cogging of titanium alloy ingots: machining the cast ingot obtained in the last step to finish the surface, heating the blank to 800-minus 1150 ℃, preserving heat for 1-10h, then carrying out hot forging cogging or hot rolling cogging for 2-10 times, heating the blank to 800-minus 1150 ℃ again after each cogging, preserving heat for 1-10h, finally preparing a square blank, and machining the square blank with the finished surface;
4) preparing a titanium alloy hot rolled plate:
heating the square blank prepared by cogging to 800-950 ℃, preserving heat for 8-180min, then carrying out hot rolling on the plate, annealing the plate after hot rolling, wherein the annealing temperature is 750-950 ℃, the annealing time is 5-150min, and then carrying out air cooling or air cooling; wherein, the deformation of hot rolling pass is controlled to be 10-50%, and the thickness of the final hot rolled plate is controlled to be 1.0-5.0 mm;
5) preparing a titanium alloy ultrathin sheet: machining the titanium alloy plate hot rolled plate obtained in the last step into a plate blank with a smooth surface, cold rolling the plate blank, wherein the cold rolling process is 2-8 rolling passes, the total deformation of each rolling pass is controlled to be 20-80%, the total deformation of each rolling pass is gradually reduced according to the rolling pass sequence, each rolling pass is annealed for 3-120min at the temperature of 750-;
6) and (3) recrystallization annealing of the titanium alloy ultrathin sheet: and (3) carrying out recrystallization annealing on the titanium alloy ultrathin plate obtained in the last step for 3-100min at the temperature of 500-900 ℃ under the protection of vacuum or inert gas, and carrying out furnace cooling or air cooling or inert gas cooling after annealing to obtain the high-plasticity titanium alloy ultrathin plate with fine grains.
Further, in the step 2), a vacuum induction skull melting furnace and a vacuum consumable electrode arc melting furnace are adopted to carry out twice fusion casting to prepare the titanium alloy ingot casting with uniform components, and the method specifically comprises the following steps: firstly, casting the ingredients prepared in the last step into an ingot by adopting a vacuum induction skull melting method, then welding the ingot into an electrode required by vacuum consumable electrode arc melting by adopting a plasma welding mode according to the size and weight of the final titanium alloy ingot, and finally, casting the electrode into the titanium alloy ingot meeting the requirements of the final size and weight by adopting the vacuum consumable electrode arc melting method.
Further, smelting by adopting a vacuum non-consumable electrode arc smelting furnace in the step 2), and repeatedly remelting for 3-7 times during smelting; and smelting by adopting a vacuum consumable electrode arc smelting furnace, and repeatedly remelting for 2-4 times during smelting.
Further, the titanium alloy comprises 0.1-0.8 wt.% of nickel element, 0.1-1.2 wt.% of niobium element, 0.1-1.2 wt.% of zirconium element, and the balance of titanium element and inevitable impurities.
The titanium alloy may also contain 0.2-0.6 wt.% of nickel, 0.2-1.0 wt.% of niobium, 0.2-1.0 wt.% of zirconium, and the balance titanium and inevitable impurities.
The titanium alloy may also contain 0.4-0.5 wt.% of nickel, 0.4-0.8 wt.% of niobium, 0.4-0.8 wt.% of zirconium, and the balance titanium and unavoidable impurities.
The nickel element, the niobium element and the zirconium element in the titanium alloy ingredient are selected from any values in percentage according to actual needs, and are not limited to the values listed in the invention.
Further, the titanium alloy raw material comprises 0A-grade sponge titanium and alloying elements.
Furthermore, the alloying elements are high-purity nickel, high-purity niobium and high-purity zirconium or intermediate alloys of nickel, niobium and zirconium.
Further, the cogging in the step 3) is performed by using a fast forging machine or a hot rolling machine.
Further, the square blank in the step 3) is a cubic square blank with the thickness of 10-100 mm.
Further, in the step 3), the blank is firstly heated to 1000 ℃ for 900-.
Further, the vacuum degree is less than or equal to 10 Pa.
The corrosion resistance and the conductivity of the titanium alloy can be further improved by adding Nb, Ni and Zr, and the corrosion resistance and the conductivity of the titanium alloy have important value for prolonging the service life of a fuel cell bipolar plate, but the room temperature plasticity of the titanium alloy is reduced due to solid solution or precipitation of a brittle and hard second phase, and the brittle and hard second phase can cause the defects of micro cracks, holes and the like in the cold rolling process of the ultrathin plate, which are not beneficial to the preparation of the ultrathin plate.
The invention provides a preparation method of a high-plasticity titanium alloy ultrathin plate for a hydrogen fuel cell bipolar plate, which controls the rolling process of a titanium alloy (Ti- (0.05-1.0 wt.%) Ni- (0.05-1.5 wt.%) Nb- (0.05-1.5 wt.%) Zr) plate with specific components, controls the titanium alloy not to separate out a brittle and hard second phase before and in the cold rolling process, and fully anneals in each rolling process, thereby obviously improving the room-temperature plasticity and cold rolling forming performance of the titanium alloy, rolling the titanium alloy ultrathin plate (with the thickness of 0.05-0.15mm) with uniform structure, smooth surface and no defect, and finally annealing the cold-rolled ultrathin plate to separate out a uniformly distributed second phase at a grain boundary to inhibit the grain growth in the annealing process, so that the finally prepared titanium alloy ultrathin plate has fine grains, and the fine grains after annealing ensure the high plasticity of the ultrathin plate, the tensile elongation of the ultrathin sheet at room temperature can reach more than 40 percent, the anisotropy is not obvious, and the plasticity requirement of the subsequent stamping forming of the titanium alloy bipolar plate for the hydrogen fuel cell can be met.
The addition amounts of nickel element, niobium element and zirconium element in the titanium alloy are required to be controlled within the composition range of the invention, and if the content of the addition elements is lower than the composition range of the invention, even if the titanium alloy ultrathin plate prepared by adopting the process of the invention is adopted, the titanium alloy ultrathin plate cannot improve the corrosion resistance of the titanium alloy due to the low element content (<0.05 wt%); if the content of the additive element is higher than the component range of the invention, the plasticity of the titanium alloy at room temperature is obviously reduced due to the solid solution of the additive element and excessive precipitation of the brittle and hard second phase, the elongation at room temperature is difficult to exceed 25 percent, and the cold rolling of the ultrathin sheet material and the subsequent stamping forming of the ultrathin sheet material are not facilitated. The selection of nickel element, niobium element and zirconium element in the titanium alloy and the limitation of the addition amount of the nickel element, the niobium element and the zirconium element in the titanium alloy are matched with the process of the invention to achieve the technical effect of the invention.
The invention has the following beneficial effects:
(1) the titanium alloy plate produced by the existing industry is not designed aiming at the application of the bipolar plate of the fuel cell, the performance of the titanium alloy plate can not meet the requirement of the bipolar plate of the hydrogen fuel cell, particularly the room temperature plasticity, and the subsequent stamping and forming requirement of the bipolar plate can not be met. The invention provides a preparation method of a high-plasticity titanium alloy ultrathin plate with specific components. The titanium alloy ultrathin plate has excellent corrosion resistance, and the room temperature plasticity of the titanium alloy ultrathin plate is far higher than that of the existing titanium alloy, and before and in the cold rolling process, as brittle and hard second phases are not precipitated, the cold rolling defect caused by the existence of the second phases is not formed, so that the cold rolling preparation of the ultrathin plate with the thickness of 0.05-0.15mm is met. The titanium alloy ultrathin plate can separate out uniformly distributed second phases at grain boundaries through annealing, thereby obviously inhibiting the grain growth in the annealing process, keeping the ultrathin plate high in plasticity due to the fine grains after annealing, still reaching more than 40% of the room-temperature tensile elongation of the ultrathin plate, basically keeping the transverse and longitudinal room-temperature strength and elongation consistent, obviously reducing the anisotropy, and meeting the plasticity requirement of the titanium alloy bipolar plate for the hydrogen fuel cell in subsequent stamping forming.
(2) The preparation of the special titanium alloy ultrathin sheet can be realized by continuously using the existing industrial preparation equipment of the titanium alloy, and no additional special equipment is added, so that the large-scale industrial production can be realized, and the special titanium alloy ultrathin sheet has important commercial value.
(3) The titanium alloy ultrathin sheet provided by the invention has wide application prospect in the fields of fuel cells and new energy automobiles, and has remarkable economic value.
Drawings
FIG. 1 is a schematic representation of a titanium alloy ultrathin sheet prepared in examples 1 and 2;
FIG. 2 shows the structure of the titanium alloy ultra-thin plate after the cold rolling process annealing and the final recrystallization annealing in examples 1 and 2;
fig. 3 is a stress-strain curve of tensile mechanical properties at room temperature of the titanium alloy ultrathin sheet prepared in example 1 and example 2.
Detailed Description
For the purpose of promoting a clear understanding of the objects, aspects and advantages of the embodiments of the invention, reference will now be made in detail to the embodiments of the present disclosure, and it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the disclosure.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention.
Example 1:
the preparation method of the high-plasticity titanium alloy ultrathin plate for the hydrogen fuel cell bipolar plate comprises the following specific steps:
(1) titanium alloy batching: the titanium alloy raw material comprises 0A-grade sponge titanium and alloying elements, wherein the alloying elements are high-purity nickel, high-purity niobium and high-purity zirconium; accurately weighing the components according to the element proportion, and uniformly mixing the components, wherein the components of the titanium alloy are 0.5 wt.% of nickel element, 0.7 wt.% of niobium element, 0.4 wt.% of zirconium element, and the balance of titanium element and inevitable impurities;
(2) preparing a titanium alloy ingot: preparing a cylindrical titanium alloy ingot with uniform components by adopting a composite fusion casting method of vacuum induction skull melting and vacuum consumable electrode arc melting; firstly, 4 cast ingots of 5 kilograms are cast by adopting a vacuum induction skull melting method, the cast ingots are processed into cylinders, then the 4 cylindrical cast ingots are welded into electrodes required by vacuum consumable electrode arc melting by adopting a plasma welding mode, and finally the electrodes are cast into titanium alloy cast ingots by adopting a vacuum consumable electrode arc melting method, so that the component uniformity of the cast ingots is ensured by adopting the composite casting method;
(3) cogging of titanium alloy ingots: processing the final ingot casting machine into a cylindrical blank, heating the blank to 1000 ℃, preserving heat for 2 hours within the temperature range, then carrying out hot forging cogging for 2 times by adopting a quick forging machine, heating the blank to 850 ℃ again between two cogging times, preserving heat for 1 hour, finally preparing a square blank, carrying out surface finishing on the square blank through mechanical processing, and finally obtaining the square blank in a cube shape with the thickness of 50 mm;
(4) preparing a titanium alloy hot rolled plate: heating the square blank prepared by cogging to 850 ℃ and preserving heat for 60 minutes, then carrying out hot rolling on the plate on a hot rolling mill, controlling the deformation of hot rolling passes to be 30%, controlling the thickness of the final hot rolled plate to be 2mm, annealing the hot rolled plate at the annealing temperature of 800 ℃ for 20 minutes, and then air-cooling.
(5) Preparing a titanium alloy ultrathin sheet: machining the titanium alloy hot rolled plate obtained in the last step into a plate blank with a smooth surface, cold rolling the plate blank by using a cold rolling mill, wherein the cold rolling process is divided into 4 rolling passes, the total deformation of each rolling pass is controlled to be 40-60%, the total deformation of each rolling pass is gradually reduced according to the rolling pass sequence (the total deformation of the 4 rolling passes is 60%, 55%, 50% and 40% respectively), annealing is carried out for 15 minutes under the inert gas protection condition at the temperature of 800 ℃ between each rolling pass, and then air cooling is carried out (the microstructure after annealing between the rolling passes is shown in a figure 2 (a)), so that the titanium alloy ultrathin plate with the thickness of 0.1mm is finally prepared, the surface of the ultrathin plate is smooth and has no cracks (shown in a figure 1 (a));
(6) and (3) recrystallization annealing of the titanium alloy ultrathin sheet: and (3) carrying out recrystallization annealing on the titanium alloy ultrathin plate obtained in the last step for 50 minutes under the protection of inert gas at the temperature of 650 ℃, and carrying out air cooling after annealing to obtain the high-plasticity titanium alloy ultrathin plate with fine grains. The grain boundary of the annealed titanium alloy ultrathin sheet forms a fine and uniformly distributed precipitated phase (the second phase precipitated after recrystallization annealing is shown in fig. 2 (b)), so that the growth of recrystallized grains of the titanium alloy is inhibited, and the recrystallized grains are uniform and fine. The titanium alloy ultrathin plate with the small grain size has ultrahigh room temperature plasticity, the room temperature tensile elongation can reach 45 percent (the stress-strain curve is shown in figure 3 (a)), the room temperature elongation in the transverse direction is basically consistent with that in the longitudinal direction, and the anisotropy is obviously reduced.
The titanium alloy ultrathin plate prepared in the embodiment 1 is made into a sample shape meeting the corrosion resistance test requirement, then the dynamic potential polarization curve (Tafel curve) is tested by adopting an electrochemical workstation under the conditions that the test temperature is 80 ℃ and the test temperature is 0.5M sulfuric acid +5ppm F ionic solution according to the national standard GB/T20042.6-2011 of the proton exchange membrane fuel cell bipolar plate characteristic test, and the corrosion current density of the sample is 97 muA/cm2Much less than the corrosion current density of pure titanium (500-600 muA/cm)2) The composite material has excellent corrosion resistance and can meet the service life requirement of the bipolar plate of the hydrogen fuel cell.
Example 2:
the preparation method of the high-plasticity titanium alloy ultrathin plate for the hydrogen fuel cell bipolar plate comprises the following specific steps:
(1) titanium alloy batching: the titanium alloy raw material comprises 0A-grade sponge titanium and alloying elements, wherein the alloying elements are high-purity nickel, high-purity niobium and high-purity zirconium. Accurately weighing according to the element proportion, and mixing and uniformly mixing, wherein the titanium alloy comprises 0.2 wt.% of nickel element, 1.2 wt.% of niobium element, 0.7 wt.% of zirconium element, and the balance of titanium element and inevitable impurities;
(2) preparing a titanium alloy ingot: a casting method of vacuum consumable electrode arc melting is adopted to prepare a titanium alloy cylindrical ingot with uniform components, and the titanium alloy ingot is repeatedly remelted for 3 times. So as to ensure the component uniformity of the cast ingot;
(3) cogging of titanium alloy ingots: and (3) processing the final ingot casting machine into a cylindrical blank, then performing high-temperature cogging by using a hot rolling machine, heating the blank to 1050 ℃, preserving heat for 3 hours within the temperature range, performing hot rolling cogging for 5 times, heating the blank to 900 ℃ again after each cogging, preserving heat for 1.5 hours, finally preparing a square blank, and mechanically processing the square blank into a square blank with a smooth surface, wherein the square blank is in a cube shape with the thickness of 20 mm.
(4) Preparing a titanium alloy hot rolled plate: heating the square blank prepared by cogging to 870 ℃ and preserving heat for 50 minutes, then carrying out hot rolling on the plate on a hot rolling mill, wherein the deformation of hot rolling passes is controlled to be 35%, the thickness of the final hot rolled plate is controlled to be 2.5mm, the plate needs to be annealed after hot rolling, the annealing temperature is 850 ℃, the annealing time is 30 minutes, and then carrying out air cooling by adopting inert gas.
(5) Preparing a titanium alloy ultrathin sheet: machining the titanium alloy hot rolled plate obtained in the last step into a plate blank with a smooth surface, cold rolling the plate blank by using a cold rolling mill, wherein the cold rolling process is 3 rolling passes, the total deformation of each rolling pass is controlled to be 50-80%, the total deformation of each rolling pass is gradually reduced according to the rolling pass sequence (the total deformation of four rolling passes is respectively 80%, 60% and 50%), and vacuum at 820 ℃ is required to be carried out between each rolling pass (the vacuum degree is less than or equal to 10 ℃)-2Pa), and then performing gas cooling by using inert gas (the microstructure after annealing between rolling passes is shown in figure 2(c), so as to finally prepare the titanium alloy ultrathin plate with the thickness of 0.1mm, wherein the surface of the ultrathin plate is smooth and has no cracks (shown in figure 1 (b)). (ii) a
(6) And (3) recrystallization annealing of the titanium alloy ultrathin sheet: the titanium alloy ultrathin sheet obtained in the last step is vacuumized at the temperature of 700 ℃ (the vacuum degree is less than or equal to 10)-2Pa), and carrying out recrystallization annealing for 40 minutes, and carrying out air cooling by using inert gas after annealing to obtain the high-plasticity titanium alloy ultrathin plate with fine grains. The grain boundary of the annealed titanium alloy ultrathin sheet forms a fine and uniformly distributed precipitated phase (the second phase precipitated after recrystallization annealing is shown in fig. 2 (d)), so that the growth of recrystallized grains of the titanium alloy is inhibited, and the recrystallized grains are uniform and fine. The titanium alloy ultrathin plate with the small grain size has ultrahigh room temperature plasticity, the room temperature tensile elongation can reach 41 percent (the stress-strain curve is shown in figure 3 (b)), the room temperature elongation in the transverse direction is basically consistent with that in the longitudinal direction, and the anisotropy is obviously reduced.
The titanium alloy ultrathin plate prepared in the embodiment 2 is made into a sample shape meeting the corrosion resistance test requirement, and then the sample is obtained by testing a potentiodynamic polarization curve (Tafel curve) under the conditions that the electrochemical workstation test temperature is 80 ℃ and the 0.5M sulfuric acid +5ppm F ionic solution is adopted according to the national standard GB/T20042.6-2011 for testing the proton exchange membrane fuel cell bipolar plate characteristicThe corrosion current density of the product is 112 muA/cm2Much less than the corrosion current density of pure titanium (500-600 muA/cm)2) The composite material has excellent corrosion resistance and can meet the service life requirement of the bipolar plate of the hydrogen fuel cell.

Claims (10)

1. A preparation method of a high-plasticity titanium alloy ultrathin plate for a hydrogen fuel cell bipolar plate is characterized by comprising the following steps:
1) titanium alloy batching: accurately weighing the components according to the element proportion, and uniformly mixing the components, wherein the components of the titanium alloy are 0.05-1.0 wt.% of nickel element, 0.05-1.5 wt.% of niobium element, 0.05-1.5 wt.% of zirconium element, and the balance of titanium element and inevitable impurities;
2) preparing a titanium alloy ingot: smelting and preparing a titanium alloy cast ingot by adopting a smelting device according to the component proportion of the titanium alloy, and smelting and casting by adopting a vacuum non-consumable electrode arc smelting furnace, or smelting and casting by adopting a vacuum induction skull smelting furnace, or smelting and casting by adopting an electron beam cold hearth furnace, or smelting and casting twice by adopting a vacuum induction skull smelting furnace and a vacuum consumable electrode arc smelting furnace to prepare the titanium alloy cast ingot with uniform components;
3) cogging of titanium alloy ingots: machining the cast ingot obtained in the last step, finishing the surface, and then performing high-temperature cogging, wherein the high-temperature cogging is to heat the blank to 800-minus 1150 ℃ for heat preservation for 1-10 hours, then performing hot forging cogging or hot rolling cogging for 2-10 times, heating the blank to 800-minus 1150 ℃ again after each cogging and preserving the heat for 1-10 hours, finally preparing a square blank, and machining the square blank with the finished surface;
4) preparing a titanium alloy hot rolled plate:
heating the square blank prepared by cogging to 800-950 ℃, preserving heat for 8-180min, then carrying out plate hot rolling, annealing the plate after hot rolling at the annealing temperature of 750-950 ℃ for 5-150min, and then carrying out air cooling or air cooling; wherein, the deformation of hot rolling pass is controlled to be 10-50%, and the thickness of the final hot rolled plate is controlled to be 1.0-5.0 mm;
5) preparing a titanium alloy ultrathin sheet: machining the titanium alloy plate hot rolled plate obtained in the last step into a plate blank with a smooth surface, cold rolling the plate blank, wherein the cold rolling process is 2-8 rolling passes, the total deformation of each rolling pass is controlled to be 20-80%, the total deformation of each rolling pass is gradually reduced according to the rolling pass sequence, each rolling pass is annealed for 3-120min at the temperature of 750-;
6) and (3) recrystallization annealing of the titanium alloy ultrathin sheet: and (3) carrying out recrystallization annealing on the titanium alloy ultrathin plate obtained in the last step for 3-100min at the temperature of 500-900 ℃ under the protection of vacuum or inert gas, and carrying out furnace cooling or air cooling or inert gas cooling after annealing to obtain the high-plasticity titanium alloy ultrathin plate with fine grains.
2. The method for preparing the high-plasticity titanium alloy ultrathin plate for the hydrogen fuel cell bipolar plate according to claim 1 is characterized in that a vacuum induction skull melting furnace and a vacuum consumable electrode arc melting furnace are adopted in the step 2) for carrying out twice casting to prepare a titanium alloy ingot with uniform components, and the method specifically comprises the following steps: firstly, casting the ingredients prepared in the last step into an ingot by adopting a vacuum induction skull melting method, then welding the ingot into an electrode required by vacuum consumable electrode arc melting by adopting a plasma welding mode according to the size and weight of the final titanium alloy ingot, and finally, casting the electrode into the titanium alloy ingot meeting the requirements of the final size and weight by adopting the vacuum consumable electrode arc melting method.
3. The preparation method of the high-plasticity titanium alloy ultrathin plate for the hydrogen fuel cell bipolar plate according to claim 1 is characterized in that in the step 2), a vacuum non-consumable electrode arc melting furnace is adopted for melting, and the melting is repeatedly carried out for 3-7 times; and smelting by adopting a vacuum consumable electrode arc smelting furnace, and repeatedly remelting for 2-4 times during smelting.
4. The method for preparing a high-plasticity titanium alloy ultrathin sheet for a hydrogen fuel cell bipolar plate according to claim 1, wherein the titanium alloy comprises 0.1 to 0.8 wt.% of nickel, 0.1 to 1.2 wt.% of niobium, 0.1 to 1.2 wt.% of zirconium, and the balance of titanium and inevitable impurities.
5. The method for preparing the high-plasticity titanium alloy ultrathin sheet for the bipolar plate of the hydrogen fuel cell as claimed in claim 1, wherein the titanium alloy raw material comprises 0A-grade titanium sponge and alloying elements.
6. The method for preparing a high-plasticity titanium alloy ultrathin sheet for a hydrogen fuel cell bipolar plate as claimed in claim 1 or 5, wherein the alloying elements are high-purity nickel, high-purity niobium and high-purity zirconium or an intermediate alloy of nickel, niobium and zirconium.
7. The method for preparing a high-plasticity titanium alloy ultrathin plate for the bipolar plate of the hydrogen fuel cell as claimed in claim 1, wherein the hot forging or hot rolling cogging is cogging by adopting a fast forging machine or a hot rolling machine.
8. The method for preparing a high-plasticity titanium alloy ultrathin plate for a hydrogen fuel cell bipolar plate as claimed in claim 1, wherein the square blank is a cubic square blank with the thickness of 10-100 mm.
9. The preparation method of the high-plasticity titanium alloy ultrathin sheet for the bipolar plate of the hydrogen fuel cell as claimed in claim 1, is characterized in that in the step 3), the blank is heated to 900-1000 ℃, the temperature is kept for 1-8h, then hot forging cogging or hot rolling cogging is carried out for 2-10 times, after each cogging, the blank needs to be heated to 900-1000 ℃ again, and the temperature is kept for 1-8h, and finally the square blank is prepared.
10. The method for preparing the high-plasticity titanium alloy ultrathin plate for the hydrogen fuel cell bipolar plate as claimed in claim 1, wherein the vacuum degree is less than or equal to 10 Pa.
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