WO2023036206A9 - 一种氢燃料电池钛金属双极板基材的制备方法 - Google Patents

一种氢燃料电池钛金属双极板基材的制备方法 Download PDF

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WO2023036206A9
WO2023036206A9 PCT/CN2022/117653 CN2022117653W WO2023036206A9 WO 2023036206 A9 WO2023036206 A9 WO 2023036206A9 CN 2022117653 W CN2022117653 W CN 2022117653W WO 2023036206 A9 WO2023036206 A9 WO 2023036206A9
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titanium
fuel cell
hydrogen fuel
bipolar plate
rolling
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PCT/CN2022/117653
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French (fr)
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WO2023036206A1 (zh
WO2023036206A8 (zh
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李渤渤
陶会发
刘茵琪
王非
裴腾
郝晓博
张强
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洛阳双瑞精铸钛业有限公司
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Priority to JP2023548997A priority Critical patent/JP2023548960A/ja
Publication of WO2023036206A1 publication Critical patent/WO2023036206A1/zh
Publication of WO2023036206A9 publication Critical patent/WO2023036206A9/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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

Definitions

  • the invention relates to the technical field of nonferrous metal processing, in particular to a method for preparing a hydrogen fuel cell titanium metal bipolar plate substrate.
  • Hydrogen fuel cell is a tool for efficient and clean utilization of hydrogen energy. It has the advantages of high energy conversion rate, low heat radiation, low noise, long battery life and zero emission. It can be widely used in automobiles, ships, aerospace and distributed power sources. Broad prospects.
  • the bipolar plate As the core component of the hydrogen fuel cell stack, the bipolar plate has multiple functions such as current collection and conduction, heat dissipation, uniform dispersion of the reaction medium, and prevention of leakage. It works in complex and harsh environments such as damp heat, electrochemical corrosion, and acid corrosion. Among them, once the bipolar plate base material corrodes and leaks, it will lead to the failure of the hydrogen fuel cell stack and safety risks. Therefore, to a large extent, the bipolar plate determines the overall performance, life and reliability of the fuel cell.
  • hydrogen fuel cell bipolar plates mainly include graphite bipolar plates and metal bipolar plates.
  • Graphite bipolar plates have shortcomings such as brittleness, difficulty in assembly, difficulty in making thinner, and low machining efficiency, which lead to large volume, low power density, and high cost of graphite bipolar hydrogen fuel cells, which limit its application in passenger cars and other industries. application prospects in the field.
  • the metal bipolar plate is mainly made of stainless steel, but the surface of stainless steel is prone to corrosion in the acidic environment of the hydrogen fuel cell, and the metal ions dissolved in the corrosion are likely to poison the catalyst, resulting in a low life and reliability of the hydrogen fuel cell. Titanium metal has the advantages of corrosion resistance and low density, which helps to improve the performance, life and reliability of hydrogen fuel cells. It is an ideal material for the metal bipolar plate base material of hydrogen fuel cells.
  • the weight of the metal bipolar plate accounts for more than 50% of the total weight of the stack, and the future market demand is huge.
  • the thickness of the base material of the hydrogen fuel cell titanium metal bipolar plate is generally 0.05 ⁇ 0.2mm, and the depth and groove width of the stamped microstructure flow channel are generally 0.2 ⁇ 2.0mm, the stamping projection area accounts for more than 50% of the total area of the board, and subsequent surface coating treatment is required, which puts forward extremely high requirements on the forming performance, dimensional accuracy and surface quality of the substrate.
  • the existing titanium substrate Poor formability in production limits its popularization and application in hydrogen fuel cells.
  • the existing titanium substrates have high production costs and difficult processing due to strict material selection, which further limits their application in hydrogen fuel cells. Promote apps. It is necessary to design and manufacture the preparation process and comprehensive performance of the titanium base material according to the subsequent processing and service requirements of the metal bipolar plate of the hydrogen fuel cell. Plate substrates have become an urgent need for industry development.
  • the purpose of the present invention is to provide a method for preparing a titanium metal bipolar plate base material for a hydrogen fuel cell, so as to prepare a high-quality, low-cost titanium metal bipolar plate base material to meet the needs of a hydrogen fuel cell for a titanium metal base material .
  • a method for preparing a titanium metal bipolar plate substrate for a hydrogen fuel cell comprising the following steps:
  • step (3) carrying out multi-pass cold rolling and semi-finished annealing to the hot-rolled titanium coil obtained in step (2) to obtain the master strip for rolling finished products;
  • step (3) Perform finished rolling on the master strip for finished rolling obtained in step (3) to obtain a titanium strip.
  • step (4) The titanium strip obtained in step (4) is first heat-treated in a continuous annealing manner under the protection of argon, and then straightened to obtain the titanium metal bipolar plate substrate for the hydrogen fuel cell.
  • the titanium sponge in step (1) is titanium sponge of grade 0 or above.
  • step (1) adopts primary EB furnace smelting.
  • step (2) is: using a continuous annealing shot blasting pickling line to first anneal the black-skinned hot-rolled titanium coil once, then perform shot blasting and pickling twice, and then perform grinding and shot blasting. Pickling treatment.
  • the annealing temperature of the semi-finished product in step (3) is 600-850°C.
  • step (4) the rolling deformation is 50%-65%, the unit tension is 200-400kg/mm 2 , the rolling speed is 50-150m/min, and the rolling force is 200-400 tons.
  • the heat treatment temperature of the continuous annealing in step (5) is 600-800° C.
  • the holding time is 0.5-2.5 min
  • the annealing tension is 0.5-2.5 KN.
  • the purity of argon in step (5) is ⁇ 99.99%.
  • the tension for straightening in step (5) is 500-1500KN, and the tensile deformation rate for straightening is 0.1%-0.3%.
  • the thickness accuracy of the hydrogen fuel cell titanium bipolar plate substrate obtained in step (5) is ⁇ 0.003mm, the unevenness is ⁇ 1.5mm/m, the yield strength (R P0.2 ) ⁇ 260MPa, and the elongation ( A 50mm ) ⁇ 30%, grain size 6-10, cupping value ⁇ 6.0mm.
  • the preparation method of the present invention When the preparation method of the present invention is applied, the double control of single impurity element content and comprehensive impurity element content is adopted to ensure the formability of the titanium metal bipolar plate base material. Since the influence of each element on the strength is different, the [O] equivalent As an index to comprehensively evaluate the impact of impurity element content on stamping performance, while ensuring the preparation of bipolar plate substrates with good formability, the upper limit of a single impurity element content is relaxed, and the material selection standard is lowered. A wider selection range is beneficial to obtain a wide range of raw materials and reduce the preparation cost.
  • the preparation method of the present invention is applied, by controlling the annealing temperature and time, the optimum grain size range of the finished product is obtained, which improves the elongation of the material and the coordinated deformation of grains during the stamping process, and at the same time aims at the forming characteristics of the metal bipolar plate , designed a comprehensive control index consisting of composition, grain size, yield strength, elongation and cupping value, which further greatly improved the forming performance of the titanium substrate and ensured the forming requirements of the special microchannel of the metal bipolar plate .
  • one-time EB smelting has high vacuum degree, high degree of superheat, good effect of removing high and low density inclusions, and has refining effect at the same time , can reduce the increment of impurity elements, so that the quality of titanium slab meets the quality control requirements, and the billet making process is shortened by more than 40% compared with the traditional 2-3 times of VAR smelting, and the finished product rate is increased by more than 5%; on the other hand, using High-temperature short-time annealing process improves annealing production efficiency, reduces argon consumption, and further reduces substrate annealing costs.
  • the preparation method of the present invention When the preparation method of the present invention is applied, the surface quality of the titanium metal bipolar plate base material is excellent, the quality is consistent and the stability is good: on the one hand, the preparation method adopts smelting with high vacuum degree, high degree of superheat, high and low density inclusion removal
  • the slab is prepared by the EB furnace with good effect and refining effect, which can significantly reduce defects such as inclusions and holes in the finished product of ultra-thin coils caused by metallurgical quality problems; on the other hand, in the process of preparing hot-rolled titanium coils, the preparation method
  • the method of pickling, grinding and pickling twice can not only ensure the complete removal of oxide skin, but also remove small and difficult-to-observe defects through mechanical grinding and multiple shot blasting chemical methods at the same time, minimizing the Defects carry over to the finished product.
  • the finished titanium coil is annealed with argon gas for a short time at high temperature.
  • the annealing time is reduced, the thickness of the oxide layer of the titanium coil is significantly improved, and the subsequent titanium metal double layer is greatly reduced. The difficulty and cost of cleaning the oxide layer before coating the plate.
  • the titanium metal bipolar plate base material obtained by the preparation method of the present invention is conducive to improving the performance, life and reliability of the hydrogen fuel cell: on the one hand, the density of titanium material is more than 40% lower than that of stainless steel, so the weight of the battery can be greatly increased Specific power density improves battery performance. In addition, titanium has excellent corrosion resistance. Compared with stainless steel metal bipolar plates, in humid heat and acidic environments, even if the coating of titanium metal bipolar plates partially falls off, it will not cause bipolar Corrosion holes in the plate and poisoning of the membrane electrode catalyst by Fe ions can greatly increase the life of the hydrogen fuel cell; on the other hand, the hydrogen fuel cell stack is composed of hundreds of bipolar plates and membrane electrodes. Any bipolar plate leakage or unevenness and thickness accuracy exceeding the standard will lead to damage to the stack.
  • the titanium substrate obtained by the preparation method of the present invention has good formability, excellent unevenness and thickness accuracy, and can greatly improve the hydrogen fuel cell when applied. reliability.
  • Example 1 Preparation of Titanium Metal Bipolar Plate Substrate for 0.15mm Hydrogen Fuel Cell
  • Sponge titanium is selected as grade 0 and above to produce 0.15mm hydrogen fuel cell titanium metal bipolar plate base material, and the sponge titanium is smelted and machined in an EB furnace to obtain a titanium slab with an Fe content of 0.020%, C
  • the N content is 0.010%
  • the N content is 0.010%
  • the O content is 0.020%
  • the [O] content is 0.062%, which can be directly used for rolling.
  • the titanium slab is hot-rolled to a thickness of 3.0mm by a steckel rolling mill, and the black-skin hot-rolled titanium coil is heat-treated and scale-removed by a continuous annealing shot-blasting pickling line, including annealing once, shot-blasting pickling twice, Use 20-high rolling mill and heat treatment furnace to carry out multi-pass cold rolling and semi-finished annealing of hot-rolled titanium coils to obtain 0.3mm annealed master strip.
  • the 0.15mm titanium strip has a rolling deformation rate of 50%.
  • the rolling parameters are shown in Table 1.
  • the titanium strip is heat-treated in an argon-protected continuous annealing furnace.
  • the heat treatment annealing temperature is 750°C, and the holding time is 2 minutes.
  • the purity of argon gas is ⁇ 99.99%, and the annealing tension is 2KN. After annealing, use a tension leveler to straighten the titanium strip. The straightening tension is 1000KN, and the tensile deformation rate is 0.20%. After leveling, take a sample, and its microstructure is shown in Figure 1 As shown, the physical and chemical properties are shown in Table 2. The finished product has excellent physical and chemical properties, good stamping performance, and is qualified after stamping. mm, roughness ⁇ 1.5mm/m, yield strength (R P0.2 ) ⁇ 260MPa, elongation (A 50mm ) ⁇ 30%, grain size 6-10, cupping value ⁇ 6.0mm.
  • Comparative Example 1 A 0.15mm hydrogen fuel cell titanium bipolar plate base material was produced by using twice-smelted forged slabs. The content of Fe was 0.040%, the content of C was 0.030%, the content of N was 0.007%, and the content of O was 0.070%. [O] When it is 0.129, all the other production processes and technological parameters are identical with embodiment 1, and the physical and chemical properties of comparative example 1 are as shown in table 2.
  • the impurity element composition of the titanium slab of Comparative Example 1 is higher than that of Example 1, resulting in the yield strength, elongation and cupping value of the finished titanium bipolar plate base material not meeting the requirements.
  • High and low elongation lead to poor formability and low cup convexity, so it is unqualified after stamping and forming, and there is a large area of cracking after forming.
  • Sponge titanium is selected as grade 0 and above to produce 0.15mm hydrogen fuel cell titanium metal bipolar plate substrate, and the sponge titanium is smelted and machined in an EB furnace to obtain a titanium slab with an Fe content of 0.037%, C
  • the N content is 0.040%, the N content is 0.004%, the O content is 0.050%, and the [O] content is 0.107%, which can be directly used for rolling.
  • the billet is hot-rolled to a thickness of 3.0mm with a steel-steel rolling mill, and the black-skin hot-rolled titanium coil is heat-treated and scale-removed, including annealing once and shot-blasting pickling twice;
  • the titanium coil is subjected to multi-pass cold rolling and semi-finished annealing to obtain a 0.2mm annealed master strip.
  • the manufacturing parameter table is shown in Table 3; the titanium strip is heat-treated in argon-protected continuous annealing furnace.
  • the straightening machine straightens the titanium belt, the straightening tension is 1500KN, and the tensile deformation rate is 0.30%. Sampling after leveling, its microstructure is shown in Figure 2, and its physical and chemical properties are shown in Table 4.
  • the finished product has excellent physical and chemical properties, good stamping performance, qualified after stamping, titanium strip unevenness ⁇ 1.0mm/m, thickness accuracy ⁇ ⁇ 0.0016mm, the finished product meets the requirements of thickness accuracy ⁇ 0.003mm, unevenness ⁇ 1.5mm/m, yield strength (R P0.2 ) ⁇ 260MPa, elongation (A 50mm ) ⁇ 30%, grain size 6-10, Cup convex value ⁇ 6.0mm requirements.
  • Comparative example 2 A 0.10mm hydrogen fuel cell titanium bipolar plate base material is produced by using twice smelted and forged slabs.
  • the content of Fe is 0.030%
  • the content of C is 0.030%
  • the content of N is 0.012%
  • the content of O is 0.04%.
  • [O] is 0.106
  • the vacuum bell annealing method is used to anneal the finished product after rolling to 0.10mm by a 20-roller rolling mill.
  • the holding temperature is 630° C. and the holding time is 2 hours.
  • Example 3 Preparation of 0.075mm hydrogen fuel cell titanium metal bipolar plate substrate
  • Sponge titanium is selected as grade 0 and above to produce 0.15mm hydrogen fuel cell titanium metal bipolar plate substrate, and the sponge titanium is smelted and machined in an EB furnace to obtain a titanium slab with an Fe content of 0.050%, C
  • the N content is 0.020%, the N content is 0.004%, the O content is 0.070%, and the [O] content is 0.119%, which can be directly used for rolling.
  • the billet is hot-rolled to a thickness of 3.0mm with a steel-steel rolling mill, and the black-skin hot-rolled titanium coil is heat-treated and scale-removed, including annealing once and shot-blasting pickling twice;
  • the titanium coil is subjected to multi-pass cold rolling and semi-finished annealing to obtain a 0.20mm annealed master strip.
  • the semi-finished annealing temperature is 850°C. It is rolled to 0.075mm by a 20-high rolling mill, and the rolling deformation rate is 62.5%.
  • the rolling parameters are shown in the table As shown in 5; the finished product heat treatment of the titanium strip is carried out in an argon-protected continuous annealing furnace, the heat treatment annealing temperature is 650°C, the holding time is 1min, the purity of the argon gas is ⁇ 99.99%, and the annealing tension is 1KN; after annealing, the titanium strip is treated with a tension leveler For leveling, the straightening tension is 500KN, and the tensile deformation rate is 0.10%. Sampling after leveling, its microstructure is shown in Figure 3, and its physical and chemical properties are shown in Table 6.
  • the finished product has excellent physical and chemical properties, good stamping performance, qualified after stamping, titanium strip unevenness ⁇ 1.0mm/m, thickness accuracy ⁇ ⁇ 0.0012mm, the finished product meets the requirements of thickness accuracy ⁇ 0.003mm, unevenness ⁇ 1.5mm/m, yield strength (R P0.2 ) ⁇ 260MPa, elongation (A 50mm ) ⁇ 30%, grain size 6-10, Cup convex value ⁇ 6.0mm requirements.
  • Comparative Example 3 A 0.075mm hydrogen fuel cell titanium bipolar plate base material was produced by using two times of melting and forging slabs, the content of Fe was 0.050%, the content of C was 0.020%, the content of N was 0.004%, and the content of O was 0.098%.
  • [O] is 0.147
  • the hot-rolled titanium coil is subjected to multi-pass cold rolling and semi-finished annealing using a 20-roll mill and a heat treatment furnace to obtain a 0.50mm annealed mother strip, which is rolled to 0.075mm by a 20-roll mill.
  • the deformation rate is 85%, and there is no tension straightening after annealing.
  • the physical and chemical properties of Comparative Example 3 are shown in Table 6.

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Abstract

一种氢燃料电池钛金属双极板基材的制备方法，定义[O] 当为钛板坯杂质元素整体含量的质量百分比，Fe、C、N、O杂质元素含量质量百分比分别为[Fe]％、[C]％、[N]％、[O]％，[O] 当计算公式为：[O] 当＝[O]％+0.5*[Fe]％+0.7*[C]％+2.5*[N]％，选用[Fe]％≤0.050％、[C]％≤0.040％、[N]％≤0.010％、[O]％≤0.080％，[O] 当≤0.120％的钛板坯，对其依次热轧、冷轧、半成品退火、成品轧制获得钛带，对钛带先在氩气保护下、以连续退火方式进行成品热处理，再经矫直获得氢燃料电池钛金属双极板基材。本发明的制备方法所制备出的氢燃料电池钛金属双极板基材品质高、成本低。

Description

一种氢燃料电池钛金属双极板基材的制备方法 技术领域
本发明涉及有色金属加工技术领域，具体涉及一种氢燃料电池钛金属双极板基材的制备方法。
背景技术
氢燃料电池是高效清洁利用氢能的工具，具有能量转化率高、热辐射低、噪音低、续航时间长以及零排放等优点，可广泛应用于汽车、船舶、航空航天及分布式电源，应用前景广阔。双极板作为氢燃料电池电堆的核心部件，起到集流导电、散热、均匀分散反应介质、防止泄露等多重功能，其工作于湿热、电化学腐蚀、酸腐蚀等多场耦合复杂恶劣环境中，双极板基材一旦发生腐蚀泄露，将导致氢燃料电池电堆失效及安全风险，因此很大程度上，双极板决定了燃料电池整体性能、寿命及可靠性。
目前，氢燃料电池双极板主要包括石墨双极板和金属双极板。石墨双极板存在易脆、组装困难、厚度难以做薄、机加工效率低等不足，导致石墨双极板氢燃料电池体积大、功率密度低、成本高，限制了其在乘用车及其它领域的应用前景。金属双极板材质以不锈钢为主，但不锈钢在氢燃料电池酸性环境中，表面易发生腐蚀，并且腐蚀所溶解的金属离子容易致使催化剂中毒，导致氢燃料电池寿命及可靠性较低。钛金属具有耐腐蚀、密度低等优势，有助于提高氢燃料电池性能、寿命及可靠性，是氢燃料电池金属双极板基材理想材料。
金属双极板重量占电堆总重量50％以上，未来市场需求巨大，氢 燃料电池钛金属双极板基材厚度一般为0.05～0.2mm，冲压微结构流道深度及槽宽一般为0.2～2.0mm，冲压投影面积占板面总面积50％以上，且后续需要表面涂层处理，对基材的成型性能、尺寸精度以及表面质量等提出了极高要求，但是，现有的钛基材在生产中成型性能较差，限制了其在氢燃料电池中的推广应用，此外现有钛基材因选材严苛而使生产成本高、加工难度大，进一步限制了其在氢燃料电池中的推广应用。需要针对氢燃料电池金属双极板后续加工及服役要求，对钛基材制备工艺及综合性能进行设计及制造，因此，为满足氢燃料电池的使用需求，开发高品质、低成本的钛金属双极板基材成为行业发展的迫切需求。
发明内容
本发明的目的在于提供一种氢燃料电池钛金属双极板基材的制备方法，以制备出高品质、低成本的钛金属双极板基材，满足氢燃料电池对钛金属基材的需求。
本发明所采用的技术方案是：
一种氢燃料电池钛金属双极板基材的制备方法，包括以下步骤：
(1)对海绵钛进行熔炼及机加工，获得钛板坯，定义[O] 当为钛板坯杂质元素整体含量的质量百分比，Fe、C、N、O杂质元素含量质量百分比分别为[Fe]％、[C]％、[N]％、[O]％，[O] 当计算公式为：
[O] 当＝[O]％+0.5*[Fe]％+0.7*[C]％+2.5*[N]％，
选取[Fe]％≤0.050％、[C]％≤0.040％、[N]％≤0.010％、[O]％≤0.080％，[O] 当≤0.120％的钛板坯用于直接轧制；
(2)对步骤(1)选取的钛板坯热轧得到黑皮态热轧钛卷，再经表面处理获得表面无氧化皮及缺陷残留的热轧钛卷；
(3)对步骤(2)获得的热轧钛卷进行多轧程冷轧及半成品退火获得成品轧制用母带；
(4)对步骤(3)获得的成品轧制用母带进行成品轧制得到钛带。
(5)对步骤(4)获得的钛带先在氩气保护下、以连续退火方式进行成品热处理，再经矫直后即得所述氢燃料电池钛金属双极板基材。
进一步地，步骤(1)中海绵钛为0级及以上海绵钛。
进一步地，步骤(1)中所述熔炼采用一次EB炉熔炼。
进一步地，步骤(2)中所述表面处理过程为：采用连续退火抛丸酸洗线对黑皮态热轧钛卷进行先退火一次、抛丸酸洗两次，再进行修磨及抛丸酸洗处理。
进一步地，步骤(3)中半成品退火的温度为600～850℃。
进一步地，步骤(4)中轧程变形量为50％～65％，单位张力为200～400kg/mm 2，轧制速度为50～150m/min，轧制力为200～400吨。
进一步地，步骤(5)中连续退火的热处理温度为600～800℃，保温时间为0.5～2.5min，退火张力为0.5～2.5KN。
进一步地，步骤(5)中氩气的纯度≥99.99％。
进一步地，步骤(5)中矫直的张力为500～1500KN，矫直的拉伸变形率为0.1％～0.3％。
进一步地，步骤(5)中获得的氢燃料电池钛金属双极板基材的 厚度精度≤±0.003mm，不平度≤1.5mm/m，屈服强度(R P0.2)≤260MPa，延伸率(A 50mm)≥30％，晶粒度6～10级，杯凸值≥6.0mm。
本发明的有益效果：
1.本发明的制备方法在应用时，采用单个杂质元素含量和综合杂质元素含量双重控制确保钛金属双极板基材的成型性能，由于各元素影响强度各有不同，采用[O] 当量作为综合评价杂质元素含量对冲压成型性能影响的一个指标，在确保制备出成型性能良好的双极板基材的同时，放宽了单个杂质元素含量上限，放低了材料选材标准，使海绵钛的选择范围更广，有利于获得广泛的原材料，降低了制备成本。
2.本发明的制备方法在应用时，通过控制退火温度和时间，获得最佳成品晶粒度范围，提高了材料延伸率及冲压过程中晶粒协调变形，同时针对金属双极板的成型特性，设计了由成分、晶粒度、屈服强度、延伸率及杯凸值组成的综合控制指标，进一步地大幅提高了钛基材的成型性能，保证了金属双极板特殊微流道的成型要求。
3.本发明的制备方法在应用时，生产效率高、成本低：一方面，通过采用一次EB熔炼，一次EB熔炼真空度高、过热度大、高低密度夹杂去除效果好，同时具有精炼作用，可减少杂质元素增量，使钛板坯的质量符合质量控制要求，且制坯流程相对于传统的2～3次VAR熔炼缩短40％以上，成材率提高5％以上；另一方面，采用高温短时退火工艺方法，提高退火生产效率，降低氩气消耗量，进一步降低基材退火成本。
4.本发明的制备方法在应用时，钛金属双极板基材的表面质量优 异、质量一致稳定性好：一方面，该制备方法采用熔炼真空度高、过热度大、高低密度夹杂去除效果好、同时具有精炼作用的EB炉制备板坯，可显著降低由于冶金质量问题导致的超薄带卷成品夹杂、孔洞等缺陷；另一方面，在热轧钛卷制备过程中，该制备方法采用2次酸洗、修磨及再酸洗方法，不仅可以保证氧化皮彻底去除，还同时通过机械修磨及多次抛丸酸洗化学法去除微小不易观察到的缺陷，最大限度的减少了缺陷遗留至成品。
5.本发明的制备方法在应用时，成品钛卷采用氩气高温短时退火，通过采用高纯度氩气保护，减少退火时间，显著改善了钛卷氧化层厚度，大幅降低了后续钛金属双极板涂层前清理氧化层难度及成本。
6.本发明的制备方法所获得的钛金属双极板基材有利于提高氢燃料电池性能、寿命及可靠性：一方面，钛材相对于不锈钢密度低40％以上，因此可大幅提高电池重量比功率密度，提高电池性能，此外，钛具有优异的耐腐蚀性，与不锈钢金属双极板相比，在湿热及酸性环境中，即使钛金属双极板涂层局部脱落，也不会导致双极板腐蚀穿洞及Fe离子毒害膜电极催化剂，因此可大幅提升氢燃料电池寿命；另一方面，氢燃料电池电堆由数百片双极板和膜电极组成，由于累计误差及应力作用，任何双极板泄露或不平度及厚度精度超标都将导致电堆损坏，本发明的制备方法所获得的钛基材成型性能好、不平度及厚度精度优异，应用时可大幅提高氢燃料电池的可靠性。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1:0.15mm氢燃料电池钛金属双极板基材的制备
选用海绵钛为0级及以上的海绵钛生产0.15mm氢燃料电池钛金属双极板基材，对海绵钛进行一次EB炉熔炼及机加工，获得钛板坯，其Fe含量为0.020％，C含量为0.010％，N含量为0.010％，O含量为0.020％，[O] 当为0.062％，可直接用于轧制。使用炉卷轧机将钛板坯坯料热轧至3.0mm厚，采用连续退火抛丸酸洗线对黑皮态热轧钛卷进行热处理及去除氧化皮，其中退火一次，抛丸酸洗两次，使用二十辊轧机及热处理炉对热轧钛卷进行多轧程冷轧及半成品退火获得0.3mm退火态母带，半成品退火温度为600℃，再采用二十辊轧机将退火态母带轧至0.15mm的钛带，轧程变形率为50％，轧制参数如表1所示，采用氩气保护连续退火炉对钛带进行成品热处理，热处理退火温度为750℃，保温时间为2min，其中氩气纯度≥99.99％，退火张力2KN，退火后使用张力矫直机对钛带进行矫直，矫直张力为1000KN，拉伸变形率为0.20％，矫平后取样，其微观组织如图1所示，理化性能如表2所示，成品理化性能优异，冲压成型性能好，冲压后合格，钛带不平度≤1.2mm/m，厚度精度≤±0.002mm，成品满足对厚度精度≤±0.003mm，不平度≤1.5mm/m，屈服强度(R P0.2)≤260MPa，延伸率(A 50mm)≥30％，晶粒度6～10级，杯凸值≥6.0mm的要求。
对比例1：采用两次熔炼锻造板坯生产0.15mm氢燃料电池钛金 属双极板基材，其Fe含量为0.040％，C含量为0.030％，N含量为0.007％，O含量为0.070％，[O] 当为0.129，其余生产过程及工艺参数与实施例1相同，对比例1的理化性能如表2所示。
表1 实施例1成品轧制参数表
Figure PCTCN2022117653-appb-000001
表2 实施例1与对比例1理化性能对比表
Figure PCTCN2022117653-appb-000002
由表2可知，对比例1的钛板坯杂质元素成分相对实施例1中偏高，导致钛金属双极板基材成品的屈服强度、延伸率及杯凸值未达到要求，由于成品屈服强度高、延伸率低导致成型性能较差，杯凸值低，因此冲压成型后不合格，成型后存在大面积开裂情况。
实施例2：0.10mm氢燃料电池钛金属双极板基材制备
选用海绵钛为0级及以上的海绵钛生产0.15mm氢燃料电池钛金属双极板基材，对海绵钛进行一次EB炉熔炼及机加工，获得钛板坯，其Fe含量为0.037％，C含量为0.040％，N含量为0.004％，O含量 为0.050％，[O] 当为0.107％，可直接用于轧制。使用炉卷轧机将坯料热轧至3.0mm厚，对黑皮态热轧钛卷进行热处理及去除氧化皮，其中退火一次，抛丸酸洗两次；使用二十辊轧机及热处理炉对热轧钛卷进行多轧程冷轧及半成品退火获得0.2mm退火态母带，半成品退火温度为750℃，采用二十辊轧机将退火态母带轧至0.10mm，轧程变形量为50％，轧制参数表如表3所示；采用氩气保护连续退火炉对钛带进行成品热处理，热处理退火温度700℃，保温时间1.5min，其中氩气纯度≥99.99％，退火张力2KN；退火后使用张力矫直机对钛带进行矫平，矫直张力1500KN，拉伸变形率0.30％。矫平后取样，其微观组织如图2所示，理化性能如表4所示，成品理化性能优异，冲压成型性能好，冲压后合格，钛带不平度≤1.0mm/m，厚度精度≤±0.0016mm，成品满足对厚度精度≤±0.003mm，不平度≤1.5mm/m，屈服强度(R P0.2)≤260MPa，延伸率(A 50mm)≥30％，晶粒度6～10级，杯凸值≥6.0mm的要求。
表3 实施例2成品轧制参数表
Figure PCTCN2022117653-appb-000003
对比例2：采用两次熔炼锻造板坯生产0.10mm氢燃料电池钛金 属双极板基材，其Fe含量为0.030％，C含量为0.030％，N含量为0.012％，O含量为0.04％，[O] 当为0.106，采用二十辊轧机轧至0.10mm后采用真空罩式退火方式进行成品退火，保温温度630℃，保温2小时，对比例2的理化性能如表4所示。
表4 实施例2与对比例2理化性能对比表
Figure PCTCN2022117653-appb-000004
由表4可知，对比例2的钛板坯杂质元素成分相对实施例2中偏高，且采用了传统的低温罩式退火方式，导致钛金属双极板基材成品的屈服强度、延伸率及杯凸值均未达到要求，成型性能较差，冲压后不合格，成型后存在大面积开裂情况。
实施例3：0.075mm氢燃料电池钛金属双极板基材制备
选用海绵钛为0级及以上的海绵钛生产0.15mm氢燃料电池钛金属双极板基材，对海绵钛进行一次EB炉熔炼及机加工，获得钛板坯，其Fe含量为0.050％，C含量为0.020％，N含量为0.004％，O含量为0.070％，[O] 当为0.119％，可直接用于轧制。使用炉卷轧机将坯料热轧至3.0mm厚，对黑皮态热轧钛卷进行热处理及去除氧化皮，其中退火一次，抛丸酸洗两次；使用二十辊轧机及热处理炉对热轧钛卷进行多轧程冷轧及半成品退火获得0.20mm退火态母带，半成品退火温度为850℃，；采用二十辊轧机轧至0.075mm，轧程变形率62.5％， 轧制参数表如表5所示；采用氩气保护连续退火炉对钛带进行成品热处理，热处理退火温度650℃，保温时间1min，其中氩气纯度≥99.99％，退火张力1KN；退火后使用张力矫直机对钛带进行矫平，矫直张力500KN，拉伸变形率0.10％。矫平后取样，其微观组织如图3所示，理化性能如表6所示，成品理化性能优异，冲压成型性能好，冲压后合格，钛带不平度≤1.0mm/m，厚度精度≤±0.0012mm，成品满足对厚度精度≤±0.003mm，不平度≤1.5mm/m，屈服强度(R P0.2)≤260MPa，延伸率(A 50mm)≥30％，晶粒度6～10级，杯凸值≥6.0mm的要求。
表5 实施例3成品轧制参数表
Figure PCTCN2022117653-appb-000005
对比例3：采用两次熔炼锻造板坯生产0.075mm氢燃料电池钛金属双极板基材，其Fe含量为0.050％，C含量为0.020％，N含量为0.004％，O含量为0.098％，[O] 当为0.147，使用二十辊轧机及热处理炉对热轧钛卷进行多轧程冷轧及半成品退火获得0.50mm退火态母带，采用二十辊轧机轧至0.075mm，成品轧程变形率85％，退火后不进行拉矫。对比例3的理化性能如表6所示。
表6 实施例3与对比例3理化性能对比表
Figure PCTCN2022117653-appb-000006
由表6可知，对比例3的钛板坯杂质元素成分相对实施例3中偏高，且成品轧程变形量较大，导致钛金属双极板基材成品的屈服强度、延伸率及杯凸值均未达到要求，成型性能较差，冲压后不合格，成型后存在大面积开裂情况。
需要说明的是，上述实施例仅用来说明本发明，但本发明并不局限于上述实施例，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明的保护范围内。

Claims (10)

  1. 一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，包括以下步骤：
    (1)对海绵钛进行熔炼及机加工，获得钛板坯，定义[O] 当为钛板坯杂质元素整体含量的质量百分比，Fe、C、N、O杂质元素含量质量百分比分别为[Fe]％、[C]％、[N]％、[O]％，[O] 当计算公式为：
    [O] 当＝[O]％+0.5*[Fe]％+0.7*[C]％+2.5*[N]％，
    选取[Fe]％≤0.050％、[C]％≤0.040％、[N]％≤0.010％、[O]％≤0.080％，[O] 当≤0.120％的钛板坯用于直接轧制；
    (2)对步骤(1)选取的钛板坯热轧得到黑皮态热轧钛卷，再经表面处理获得表面无氧化皮及缺陷残留的热轧钛卷；
    (3)对步骤(2)获得的热轧钛卷进行多轧程冷轧及半成品退火获得成品轧制用母带；
    (4)对步骤(3)获得的成品轧制用母带进行成品轧制得到钛带；
    (5)对步骤(4)获得的钛带先在氩气保护下、以连续退火方式进行成品热处理，再经矫直后即得所述氢燃料电池钛金属双极板基材。
  2. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(1)中海绵钛为0级及以上海绵钛。
  3. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(1)中所述熔炼采用一次EB炉熔炼。
  4. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(2)中所述表面处理过程为：采用连续退火抛丸酸洗线对黑皮态热轧钛卷进行先退火一次、抛丸酸洗两次，再进行修磨及抛丸酸洗处理。
  5. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(3)中半成品退火的温度为600～850℃。
  6. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(4)中轧程变形量为50％～65％，单位张力为200～400kg/mm 2，轧制速度为50～150m/min，轧制力为200～400吨。
  7. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(5)中连续退火的热处理温度为600～800℃，保温时间为 0.5～2.5min，退火张力为0.5～2.5KN。
  8. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(5)中氩气的纯度≥99.99％。
  9. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(5)中矫直的张力为500～1500KN，矫直的拉伸变形率为0.1％～0.3％。
  10. 如权利要求1所述的一种氢燃料电池钛金属双极板基材的制备方法，其特征在于，步骤(5)中获得的氢燃料电池钛金属双极板基材的厚度精度≤±0.003mm，不平度≤1.5mm/m，屈服强度(R P0.2)≤260MPa，延伸率(A 50mm)≥30％，晶粒度6～10级，杯凸值≥6.0mm。
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CN107502751B (zh) * 2017-07-17 2019-03-01 洛阳双瑞精铸钛业有限公司 一种用屑状和板状纯钛残料熔炼回收获得ta2扁锭的方法
CN107723638B (zh) * 2017-09-08 2019-09-06 洛阳双瑞精铸钛业有限公司 一种深冲用钛板的制备方法
CN108165822B (zh) * 2018-02-10 2020-04-14 洛阳双瑞精铸钛业有限公司 一种低强度、易成型焊管用ta2冷轧钛带的制备方法
CN112122382B (zh) * 2020-07-23 2022-04-12 洛阳双瑞精铸钛业有限公司 一种轧制复合用宽幅超薄冷轧钛带卷制备工艺方法
CN112122340A (zh) * 2020-07-23 2020-12-25 洛阳双瑞精铸钛业有限公司 一种提高冷轧钛带卷得料率的工艺方法
CN113948721A (zh) * 2021-09-08 2022-01-18 洛阳双瑞精铸钛业有限公司 一种氢燃料电池钛金属双极板基材的制备方法

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