WO2023284596A1 - Revêtement composite en solution solide de type phase max à haute conductivité, résistant à la corrosion et à longue durée de vie, et procédé de préparation associé et utilisation correspondante - Google Patents

Revêtement composite en solution solide de type phase max à haute conductivité, résistant à la corrosion et à longue durée de vie, et procédé de préparation associé et utilisation correspondante Download PDF

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WO2023284596A1
WO2023284596A1 PCT/CN2022/104020 CN2022104020W WO2023284596A1 WO 2023284596 A1 WO2023284596 A1 WO 2023284596A1 CN 2022104020 W CN2022104020 W CN 2022104020W WO 2023284596 A1 WO2023284596 A1 WO 2023284596A1
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max phase
composite coating
phase solid
bipolar plate
corrosion
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PCT/CN2022/104020
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Chinese (zh)
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汪爱英
马冠水
王振玉
王丽
陈仁德
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中国科学院宁波材料技术与工程研究所
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5893—Mixing of deposited material
    • 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
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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

  • This application belongs to the technical field of metal surface coating protection, and relates to a MAX phase solid-solution composite coating, its preparation method and application, especially to a high-conductivity, corrosion-resistant, long-life Ti 2 (Al 1-x Sn x )C MAX Phase solid solution composite coating and its preparation method and application.
  • PEMFCs proton exchange membrane fuel cells
  • the high interface contact resistance and corrosion of the core component metal bipolar plate are the key technical bottlenecks that determine the battery life.
  • the use of surface coating technology can improve the electrical conductivity and corrosion resistance of the metal plate while maintaining the excellent performance of the metal plate itself.
  • M n+1 AX n phase As an emerging cermet material, has a close-packed hexagonal layered structure, and the layers rely on metal bonds between M atoms and A atoms.
  • the unique layered structure and bonding characteristics enable the MAX phase to have both the electrical and thermal conductivity of metals and ceramics, high temperature oxidation resistance, and high strength.
  • the oxide film formed by the oxidation of the MAX phase coating will lead to an increase in the interface contact resistance after corrosion, which seriously affects the life and performance of the battery.
  • the deposition of sputtering composite targets by DC magnetron sputtering technology is the main method to prepare solid solution MAX phase coatings, but the ionization rate of the targets is insufficient, the deposition rate is low, and the prepared coatings will have columnar structure defects, corrosion, etc.
  • the ionic medium will corrode the substrate through the pores between the columnar structures and accelerate the degradation of the performance of the plate.
  • the main purpose of this application is to provide a high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating, its preparation method and application, so as to overcome the deficiencies of the prior art.
  • the embodiment of the present application provides a method for preparing a high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating, which includes:
  • Ti-Al-C layers and Ti-Sn-C layers alternately deposit Ti-Al-C layers and Ti-Sn-C layers on the surface of the metal bipolar plate substrate, thereby forming an alternate stack of Ti-Al-C/Ti-Sn-C layer, wherein the alternate stacking of Ti-Al-C/Ti-Sn-C includes 2 to 10 alternating stacking periodic layers, and each alternate stacking periodic layer includes a Ti-Al-C layer and a Ti-Sn-C layer ;
  • Ti-Al-C/Ti-Sn-C alternate lamination so as to form a Ti 2 (Al 1-x Sn x )C MAX phase solid solution composite coating, that is, a high-conductivity, corrosion-resistant and long-lasting Lifetime MAX phase solid solution composite coating, where 0 ⁇ x ⁇ 1.
  • the embodiment of the present application also provides a high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating prepared by the aforementioned method, and the conductivity of the high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating is 3.1 ⁇ 10 4 ⁇ 10 6 ⁇ -1 ⁇ m -1 .
  • the embodiment of the present application also provides the use of the aforementioned high-conductivity, corrosion-resistant, long-life MAX phase solid-solution composite coating in the preparation of fuel cells.
  • the embodiment of the present application also provides a method for modifying the surface of a metal bipolar plate of a hydrogen fuel cell, which includes: depositing on the surface of a metal bipolar plate of a hydrogen fuel cell using the aforementioned method to form a solid-solution composite of a high-conductivity, corrosion-resistant, and long-life MAX phase Coating, so as to realize the modification treatment of hydrogen fuel cell metal bipolar plate.
  • This application prepares a Ti 2 (Al 1-x Sn x )C MAX phase solid solution composite coating on the surface of the metal bipolar plate substrate, which not only improves the corrosion resistance of the substrate, but also improves the corrosion resistance of the substrate under long-term acidic working conditions. It can maintain a high electrical conductivity under acidic conditions, because the Ti 2 (Al 1-x Sn x )C MAX phase solid solution composite coating can form a SnO 2 passivation film under acidic conditions.
  • SnO 2 is a kind of The n-type semiconductor that can exist stably in the medium is also an excellent transparent conductive material, which can improve the corrosion resistance of the substrate without reducing its electrical conductivity;
  • the target power, power frequency, pulse and other processes are optimized to avoid magnetic Due to the limitation of insufficient thermal capacity of the control source and the inability to work in a high-power state, the controllable adjustment of high plasma density, high ionization rate and deposited particle energy is realized, and the generation of columnar defects is reduced, which is conducive to the formation of dense coatings. At the same time, this alternate stacked structure is conducive to the mutual combination of Ti, Al and C atoms during the annealing process, so that the formed MAX phase has a higher purity.
  • the alternate stacked structure of Ti-Al-C/Ti-Sn-C avoids the penetration of columnar defects formed during the deposition process, prolongs the corrosion channel of the solution, and makes the Ti 2 (Al 1-x Sn x )
  • the corrosion resistance of the C MAX phase solid solution composite coating is further improved.
  • Fig. 1 is the scanning electron micrograph of the Ti 2 (Al 0.5 Sn 0.5 ) C MAX phase solid solution composite coating prepared in Example 1 of the present application;
  • Fig. 2 is the energy spectrogram of the chemical composition of the Ti 2 (Al 0.5 Sn 0.5 ) C MAX phase solid solution composite coating prepared in Example 1 of the present application;
  • Fig. 3 is the energy spectrogram of the chemical composition of the Ti 2 (Al 0.6 Sn 0.4 ) C MAX phase solid solution composite coating prepared in Example 2 of the present application;
  • Fig. 4 is the energy spectrogram of the chemical composition of the Ti 2 (Al 0.3 Sn 0.7 ) C MAX phase solid solution composite coating prepared in Example 3 of the present application;
  • Figure 5 is a comparison chart of the constant potential corrosion performance test of the Ti2 (Al1 - xSnx )C MAX phase solid solution composite coating prepared in Examples 1-3 of the present application;
  • Fig. 6 is a graph showing the changes in contact resistance before and after corrosion of the Ti 2 (Al 1-x Sn x )C MAX phase solid solution composite coating prepared in Examples 1-3 of the present application.
  • One aspect of the embodiments of the present application provides a method for preparing a high-conductivity, corrosion-resistant, and long-life MAX phase solid-solution composite coating, including:
  • Ti-Al-C layers and Ti-Sn-C layers alternately deposit Ti-Al-C layers and Ti-Sn-C layers on the surface of the metal bipolar plate substrate, thereby forming an alternate stack of Ti-Al-C/Ti-Sn-C layer, wherein the alternate stacking of Ti-Al-C/Ti-Sn-C includes 2 to 10 alternating stacking periodic layers, and each alternate stacking periodic layer includes a Ti-Al-C layer and a Ti-Sn-C layer ;
  • Ti-Al-C/Ti-Sn-C alternate lamination so as to form a Ti 2 (Al 1-x Sn x )C MAX phase solid solution composite coating, that is, a high-conductivity, corrosion-resistant and long-lasting Lifetime MAX phase solid solution composite coating, where 0 ⁇ x ⁇ 1.
  • the preparation method specifically includes: placing the metal bipolar plate substrate in a vacuum chamber, using TiAl alloy targets and TiSn alloy targets as targets, and using CH4 and inert gases as working gases , using high-power pulsed magnetron sputtering technology, depositing and forming alternate Ti-Al-C/Ti-Sn-C stacks on the surface of the metal bipolar plate substrate, wherein the bias voltage of the metal bipolar plate substrate is -30 ⁇ -150V, high-power pulse duty ratio of 1-15%, high-power pulse frequency of 100-150Hz, pulse width of 20-150 ⁇ s, vacuum chamber pressure of 0.1-0.3Pa, deposition time of 5.0-100min.
  • the base bias voltage of the metal bipolar plate is -90--120V, and the high-power pulse duty cycle is 5-10%.
  • the process conditions for depositing and forming the Ti-Al-C layer include: using a TiAl alloy target as the target material, using CH 4 and an inert gas as the working gas, and the heating temperature of the metal bipolar plate substrate is 50-100°C,
  • the sputtering power of the TiAl alloy target is 800-2000W
  • the flow rate of CH 4 is 2.0-20 sccm
  • the flow rate of inert gas is 100-200 sccm
  • the deposition time is 5.0-100 min.
  • the process conditions for depositing and forming the Ti-Sn-C layer include: using a TiSn alloy target as a target material, using CH4 and an inert gas as a working gas, and the heating temperature of the metal bipolar plate substrate
  • the temperature is 50-100°C
  • the sputtering power of TiSn alloy target is 400-1000W
  • the flow rate of CH 4 is 2.0-20sccm
  • the flow rate of inert gas is 100-200sccm
  • the deposition time is 5.0-100min.
  • the inert gas includes argon.
  • the preparation method specifically includes: treating the Ti-Al-C/Ti- Sn- C is alternately stacked and heat-treated for 2.0-20 hours, so as to obtain the Ti 2 (Al 1-x Sn x )C MAX phase solid solution composite coating.
  • the thickness of the alternate Ti-Al-C/Ti-Sn-C stack is 0.1-5 ⁇ m.
  • the material of the metal bipolar plate substrate includes any one or a combination of two or more of zirconium alloy, aluminum, aluminum alloy, titanium, titanium alloy, and stainless steel, but is not limited thereto.
  • the preparation method further includes: before depositing the alternate stack of Ti-Al-C/Ti-Sn-C, ultrasonically cleaning the metal bipolar plate substrate, glow discharge Etching treatment.
  • the preparation method of the high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating specifically includes: using a metal bipolar plate as a substrate, using high-power pulse magnetron sputtering technology, using TiAl alloy target and TiSn alloy target are sequentially used as magnetron sputtering targets (for providing Ti, Al and Sn sources), CH 4 and Ar gas are used as working gases, and Ti-Al- C coating, then deposit Ti-Sn-C coating, and then alternately obtain Ti-Al-C/Ti-Sn-C alternate stacks, which are also recorded as (Ti-Al-C/Ti-Sn-C) y layer, wherein 10 ⁇ y ⁇ 2; then, vacuum heat treatment is performed to obtain Ti 2 (Al 1-x Sn x )C(0 ⁇ x ⁇ 1) MAX phase solid solution composite coating.
  • the surface of the metal bipolar plate substrate is ultrasonically cleaned with acetone and ethanol for 10 minutes, and then glow discharge etching is performed.
  • the bias voltage of the metal bipolar plate substrate is -30V ⁇ -150V.
  • the process conditions for depositing the (Ti-Al-C/Ti-Sn-C) y layer include: the high-power pulse duty ratio is 1%-15%; the high-power pulse frequency is 100Hz-150Hz, and the pulse width is 20 ⁇ s ⁇ 150 ⁇ s.
  • the heating temperature of the metal bipolar plate substrate is 50-100°C.
  • the sputtering power of the TiAl alloy target is 800-2000W
  • the sputtering power of the TiSn alloy target is 400-1000W
  • the deposition time is 15min- 100min.
  • the feed flow rate of working gas CH is 2sccm ⁇ 20sccm
  • the feed flow rate of argon is 100sccm ⁇ 200sccm
  • the deposition chamber pressure It is 0.1Pa ⁇ 0.3Pa.
  • the heat treatment temperature is 450°C-750°C, and the time is 2.0h-20h.
  • Another aspect of the embodiments of the present application also provides a high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating prepared by the aforementioned method, the conductivity of the high-conductivity, corrosion-resistant and long-life MAX phase solid-solution composite coating is 3.1 ⁇ 10 6 to 4 ⁇ 10 6 ⁇ ⁇ 1 ⁇ m ⁇ 1 .
  • Another aspect of the embodiments of the present application also provides the use of the aforementioned high-conductivity, corrosion-resistant, and long-life MAX phase solid-solution composite coating in preparing a fuel cell.
  • Another aspect of the embodiment of the present application also provides a method for modifying the surface of a hydrogen fuel cell metal bipolar plate, which includes: using the aforementioned method to deposit on the surface of a hydrogen fuel cell metal bipolar plate to form a highly conductive, corrosion-resistant and long-life MAX Phase solid solution composite coating, so as to realize the modification of metal bipolar plate of hydrogen fuel cell.
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 (Al 0.5 Sn 0.5 )C MAX phase solid solution composite coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • the Ti-Al-C layer is deposited by high-power pulsed magnetron sputtering technology, wherein the Ti 0.5 Al 0.5 alloy target provides the Ti source and the Al source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon gas The flow rate is 100sccm, the high-power pulse duty ratio is 1%, the sputtering power of the Ti 0.5 Al 0.5 alloy target is 2000W, the bias voltage of the substrate is -50V, the deposition time is 10min, and the Ti-Al-C layer is deposited;
  • the Ti-Sn-C layer is re-deposited by high-power pulsed magnetron sputtering technology, wherein the Ti 0.2 Sn 0.8 alloy target provides the Ti source and the Sn source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon The gas flow rate is 100sccm, the high-power pulse duty ratio is 1%, the sputtering power of the Ti 0.2 Sn 0.8 alloy target is 1000W, the bias voltage of the substrate is -50V, the deposition time is 15min, and the Ti-Sn-C layer is deposited;
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 (Al 0.6 Sn 0.4 )C MAX phase solid-solution composite coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • the Ti-Al-C layer is deposited by high-power pulsed magnetron sputtering technology, wherein the Ti 0.3 Al 0.7 alloy target provides the Ti source and the Al source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon gas The flow rate is 100sccm, the high-power pulse duty ratio is 1%, the sputtering power of the Ti 0.3 Al 0.7 alloy target is 2000W, the bias voltage of the substrate is -100V, the deposition time is 15min, and the Ti-Al-C layer is deposited;
  • the Ti-Sn-C layer is re-deposited by high-power pulsed magnetron sputtering technology, wherein the Ti 0.5 Sn 0.5 alloy target provides the Ti source and the Sn source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon The gas flow rate is 100sccm, the high-power pulse duty ratio is 1%, the sputtering power of the Ti 0.5 Sn 0.5 alloy target is 1000W, the bias voltage of the substrate is -100V, the deposition time is 20min, and the Ti-Sn-C layer is deposited;
  • Steps (2) and (3) were repeated 5 times to obtain alternate stacks of Ti-Al-C/Ti-Sn-C, namely (Ti-Al-C/Ti-Sn-C) 6 layers;
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 (Al 0.3 Sn 0.7 )C MAX phase solid-solution composite coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • the Ti-Al-C layer is deposited by high-power pulsed magnetron sputtering technology, wherein the Ti 0.7 Al 0.3 alloy target provides the Ti source and the Al source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon gas The flow rate is 100sccm, the high-power pulse duty ratio is 1%, the Ti 0.7 Al 0.3 alloy target sputtering power is 2000W, the bias voltage of the substrate is -100V, the deposition time is 15min, and the Ti-Al-C layer is deposited;
  • the Ti-Sn-C layer is re-deposited by high-power pulsed magnetron sputtering technology, wherein the Ti 0.3 Sn 0.7 alloy target provides the Ti source and the Sn source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon The gas flow rate is 150sccm, the high-power pulse duty ratio is 1%, the sputtering power of the Ti 0.3 Sn 0.7 alloy target is 2000W, the bias voltage of the substrate is -100V, the deposition time is 15min, and the Ti-Sn-C layer is deposited;
  • Steps (2) and (3) were repeated 8 times to obtain alternate stacks of Ti-Al-C/Ti-Sn-C, namely (Ti-Al-C/Ti-Sn-C) 9 layers;
  • Fig. 6 is the change diagram of the contact resistance of the coatings prepared in the above-mentioned embodiment 1, embodiment 2 and embodiment 3 before and after constant potential corrosion for 12h, as can be seen from Fig. to 3.3m ⁇ cm 2 , which is mainly because the oxide film SnO 2 formed after corrosion has good electrical conductivity, so its electrical conductivity does not change much.
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 (Al 0.6 Sn 0.4 ) C MAX phase solid solution coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • the Ti-Al/Sn-C layer was deposited by high-power pulsed magnetron sputtering technology, in which the Ti 0.5 Al 0.3 Sn 0.2 alloy target provided the Ti source and the Al source, and the gas CH 4 provided the C source, and the CH 4 flow rate was 2sccm, argon gas flow rate of 100sccm, high power pulse duty ratio of 1%, Ti 0.5 Al 0.3 Sn 0.2 alloy target sputtering power of 2000W, substrate bias of -100V, deposition time of 15min, Ti-Al was deposited /Sn-C layer;
  • the solution is 0.5M H 2 SO 4 +5ppm HF solution
  • the temperature of the solution is 80°C
  • the results show that due to the lack of alternate lamination structure, it is not conducive to the mutual combination of Ti, Al and C atoms during the annealing process, so that the purity of the formed MAX phase is only 70%, and the interface contact resistance is 11m ⁇ ⁇ cm 2 , the conductivity is far worse than that of the practical case.
  • the structure without alternate lamination increases the corrosion channel of the solution, so that the corrosion current density is 1 ⁇ 10 -5 Acm -2 after the constant potential acceleration test for 24 hours, and the corrosion resistance is far worse than that of the implementation case.
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 (Al 0.3 Sn 0.7 ) C MAX phase solid solution coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • the Ti-Al-C layer was deposited by DC magnetron sputtering technology, in which the Ti 0.7 Al 0.3 alloy target provided the Ti source and the Al source, the gas CH 4 provided the C source, the CH 4 flow rate was 2 sccm, and the Ar gas flow rate was 100sccm, Ti 0.7 Al 0.3 alloy target sputtering power is 2000W, substrate bias is -100V, deposition time is 15min, Ti-Al-C layer is deposited;
  • the Ti-Sn-C layer is re-deposited by DC magnetron sputtering technology, wherein the Ti 0.3 Sn 0.7 alloy target provides the Ti source and the Sn source, the gas CH 4 provides the C source, the CH 4 flow rate is 2 sccm, and the argon gas flow rate
  • the sputtering power of the Ti 0.3 Sn 0.7 alloy target is 150sccm
  • the sputtering power of the Ti 0.3 Sn 0.7 alloy target is 2000W
  • the bias voltage of the substrate is -100V
  • the deposition time is 15min
  • the Ti-Sn-C layer is deposited;
  • Steps (2) and (3) were repeated 8 times to obtain alternate stacks of Ti-Al-C/Ti-Sn-C, namely (Ti-Al-C/Ti-Sn-C) 9 layers;
  • the solution is 0.5M H 2 SO 4 +5ppm HF solution
  • the temperature of the solution is 80°C
  • the results show that the interface contact resistance is 15m ⁇ cm 2 due to the insufficient density of the coating prepared by the high-power pulse magnetron sputtering technology, and the conductivity is far worse than that of the practical case.
  • the constant potential acceleration experiment was tested for 24 hours
  • the post-corrosion current density is 6 ⁇ 10 -6 Acm -2 , and the corrosion resistance is far worse than that of the practical case.
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 AlC MAX phase coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • the Ti-Al-C layer is deposited by high-power pulsed magnetron sputtering technology, and the TiAl alloy target is used as the magnetron sputtering target to provide Ti and Al sources, and the gas CH4 provides the C source, and the CH4 flow rate is 1sccm , the argon flow rate is 40 sccm, the gas CH4 provides the C source, the CH4 flow rate is 2 sccm, the argon gas flow rate is 100 sccm, the high-power pulse duty cycle is 1%, the TiAl alloy target sputtering power is 2000W, and the bias voltage of the substrate is -100V, the deposition time is 15min, and the Ti-Al-C layer is deposited;
  • a three-electrode electrochemical test system was used to test the corrosion resistance of the substrate of the Ti 2 AlC MAX phase coating on the surface obtained in the above comparative example.
  • the solution was 0.5M H 2 SO 4 +5ppm HF solution, and the solution temperature was 80°C.
  • the results showed Since no conductive SnO 2 was formed after the electrochemical corrosion test, the corrosion current density was 9 ⁇ 10 -4 Acm -2 after the constant potential acceleration test for 24 hours, the corrosion resistance was far worse than that of the practical case, and the interface contact resistance increased to 8m ⁇ cm 2 , the conductivity is far worse than the implementation case.
  • the substrate is a 316L stainless steel bipolar plate used in a proton exchange membrane fuel cell, and the preparation method of the Ti 2 SnC MAX phase coating on the surface of the substrate is as follows:
  • the surface of the metal substrate after grinding and polishing is firstly ultrasonically cleaned with acetone and ethanol for 10 minutes.
  • 50 sccm of argon gas set the linear anode ion source voltage to 1200V, the substrate bias to -200V, and use ionized argon ions to etch the substrate for 30 minutes;
  • TiSn alloy target provides Ti source and Sn source
  • gas CH4 provides C source
  • CH4 flow rate is 2sccm
  • argon gas flow rate is 150sccm
  • the high power pulse duty ratio is 1%
  • the sputtering power of the TiSn alloy target is 2000W
  • the bias voltage of the substrate is -100V
  • the deposition time is 15min
  • the Ti-Sn-C layer is deposited
  • the solution is 0.5M H 2 SO 4 +5ppm HF solution, the solution temperature is 80°C, and the constant potential
  • the 24h test results of the accelerated test show that the passivation film SnO 2 formed after the test is not dense enough, resulting in continuous corrosion of the liquid contact sample, resulting in a corrosion current density of 7 ⁇ 10 -6 Acm -2 , and the corrosion resistance is far worse than that of the actual case.

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Abstract

Revêtement composite en solution solide de type phase MAX à haute conductivité, résistant à la corrosion et à longue durée de vie, procédé de préparation associé et utilisation correspondante. Le procédé de préparation consiste : à déposer en alternance, à l'aide d'une technologie de pulvérisation magnétron par impulsions de haute puissance, une couche de Ti-Al-C et une couche de Ti-Sn-C sur la surface d'un substrat de plaque bipolaire métallique, afin de former une stratification alternée de Ti-Al-C/Ti-Sn-C ; et à soumettre la stratification alternée de Ti-Al-C/Ti-Sn-C à un traitement thermique sous vide afin de former un revêtement composite en solution solide de type phase MAX de Ti2(Al1-xSnx)C.
PCT/CN2022/104020 2021-07-11 2022-07-06 Revêtement composite en solution solide de type phase max à haute conductivité, résistant à la corrosion et à longue durée de vie, et procédé de préparation associé et utilisation correspondante WO2023284596A1 (fr)

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