CN117305878A - High-conductivity strong corrosion-resistant coating for bipolar plate of PEM (PEM) electrolytic tank and preparation method thereof - Google Patents
High-conductivity strong corrosion-resistant coating for bipolar plate of PEM (PEM) electrolytic tank and preparation method thereof Download PDFInfo
- Publication number
- CN117305878A CN117305878A CN202311345827.1A CN202311345827A CN117305878A CN 117305878 A CN117305878 A CN 117305878A CN 202311345827 A CN202311345827 A CN 202311345827A CN 117305878 A CN117305878 A CN 117305878A
- Authority
- CN
- China
- Prior art keywords
- coating
- bipolar plate
- nitriding
- pem
- conductivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 138
- 239000011248 coating agent Substances 0.000 title claims abstract description 132
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 230000007797 corrosion Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005121 nitriding Methods 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 54
- 238000000137 annealing Methods 0.000 claims description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000004767 nitrides Chemical class 0.000 claims description 22
- 238000004544 sputter deposition Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 8
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- -1 transition metal nitride Chemical class 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 34
- 239000012528 membrane Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000149 penetrating effect Effects 0.000 abstract description 3
- 150000003608 titanium Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 29
- 239000002131 composite material Substances 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 16
- 238000005530 etching Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- AEJRTNBCFUOSEM-UHFFFAOYSA-N 3-Methyl-1-phenyl-3-pentanol Chemical compound CCC(C)(O)CCC1=CC=CC=C1 AEJRTNBCFUOSEM-UHFFFAOYSA-N 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/036—Bipolar electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a high-conductivity strong corrosion-resistant coating for a bipolar plate of a PEM (proton exchange membrane) electrolytic cell and a preparation method thereof, aiming at the surface characteristics of a bipolar plate flow channel of the PEM electrolytic cell and the technical characteristics of magnetron sputtering, firstly, ion nitriding is adopted to carry out surface pretreatment to form a first protection layer which is uniformly distributed, the surface morphology and the structure of a titanium-based bipolar plate are reconstructed, then, the magnetron sputtering technology is adopted to prepare a second protection layer with fine and compact grains, and the problem of poor quality of the PEM electrolytic cell bipolar plate coating prepared by magnetron sputtering is solved. The nanocrystalline coating prepared by the method has compact structure, prevents corrosive medium from penetrating through the coating to corrode the substrate, has low lattice mismatch degree, improves the binding force between the coating and the substrate, has good conductivity, and further reduces the contact resistance of the bipolar plate.
Description
Technical Field
The invention belongs to the field of hydrogen production by PEM (proton exchange membrane) electrolysis of water, and particularly relates to a bipolar plate high-conductivity strong corrosion-resistant coating of a PEM (proton exchange membrane) electrolysis tank and a preparation method thereof.
Background
Hydrogen energy is an important component of future energy systems, with the use of renewable energy sources to produce hydrogen being a major direction of development. The proton exchange membrane water electrolyzer (Proton Exchange Membrane electrolyzer Cell, PEMEC, PEM electrolyzer for short) can well solve the fluctuation and intermittence problems of renewable energy sources such as wind power, photovoltaic power generation and the like, and is a green hydrogen production device with the most development potential. The working environment of the bipolar plate of the PEM electrolytic tank has strong acidity (pH value is 2-4), high potential (1.5-2V) and strong oxidation (O is produced by the anode) 2 ) And the like, therefore, the bipolar plate material is required to have good corrosion resistance, high conductivity and long life. Currently, research and commercial applications are mainly focused on titanium-based bipolar plates, however, titanium materials tend to form passivation films on the oxygen side to increase contact resistance, thereby increasing overpotential and decreasing water electrolysis efficiency. The corrosion resistance and the conductivity of the titanium-based bipolar plate can be obviously improved by coating noble metal coatings such as Pt, it and the like on the surface of the bipolar plate, but the cost is high and scarce, and the requirements of large-scale production and application of hydrogen energy in the future are difficult to meet. Therefore, developing bipolar plate coating modification technology that combines high conductivity, strong corrosion resistance and significantly reduced cost is one of the key issues that PEM electrolysers must address for large scale applications.
Titanium nitride (TiN) has corrosion resistance and high conductivity, is an important candidate material for a bipolar plate coating of a PEM (proton exchange membrane) electrolytic cell, and the most common method for preparing the TiN coating on the surface of the titanium-based bipolar plate is a magnetron sputtering coating method, and the working principle is that electrons collide with argon atoms under the action of an electric field to ionize the electrons so as to generate Ar ions with positive charges and electrons with negative charges, the Ar ions fly to a cathode target in an accelerating way under the action of the electric field, the target surface is bombarded with high energy, sputtering occurs, the sputtered target components are deposited on the surface of a substrate under the action of the electric field, and the film/coating is formed by gradual growth. However, magnetron sputtering coating has poor plating coiling property, and the coating quality, the film-based bonding strength and the electrochemical characteristics are directly related to the surface appearance of the substrate. Therefore, fine optimization of surface pretreatment such as cleaning, grinding, polishing and the like is required to improve the quality of the magnetron sputtering coating.
Typically, the bipolar plates of PEM cells have channels of "ridge-and-groove" configuration distributed across the surface and having a depth of about 0.3 to about 1.5mm and a width of about 0.5 to about 2mm. In the process of preparing the coating by magnetron sputtering, the side wall of the flow channel structure is perpendicular to the target, the coating tends to grow unevenly and even deposit no coating, and the corrosion resistance of the bipolar plate is greatly influenced. In addition, the surface defects of the base material are more after the bipolar plate runner is processed, and the compactness of the coating and the binding force of the film base can be adversely affected. In order to solve the problems, researchers prepare noble metal coatings such as Pt and Ir on the surface of a bipolar plate by an electroplating method, and the electroplating coatings have the defects of pinholes, impurity elements and the like although the uniformity is good, and the coatings are easy to fall off after long-term service, so that the durability is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a high-conductivity and strong-corrosion-resistance coating for a bipolar plate of a PEM (proton exchange membrane) electrolytic cell and a preparation method thereof, so as to solve the problems that the coating of the bipolar plate of the PEM electrolytic cell is easy to fall off, and the binding force of the coating and the binding force of the surface of a polar plate are not strong in the prior art.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a preparation method of a high-conductivity strong corrosion-resistant coating of a bipolar plate of a PEM electrolytic cell comprises the steps of preparing a titanium nitride nanocrystalline film on the surface of a titanium-based bipolar plate through nitriding; sputtering a metal nitride nanocrystalline coating on the surface of the titanium nitride nanocrystalline film, wherein the metal nitride nanocrystalline is a transition metal nitride nanocrystalline; preparing a high-conductivity strong corrosion-resistant coating on the surface of the titanium-based bipolar plate;
the grain size of the titanium nitride nanocrystalline film is 5-20 nm; the grain size of the metal nitride nanocrystalline coating is 5-40 nm.
The invention further improves that:
preferably, in the nitriding process, the side with the flow channels distributed faces the anode plate, and the distance between the side with the flow channels distributed and the anode plate is less than or equal to 100mm.
Preferably, the nitriding time is 2-6h, the nitriding pressure is 1-30Pa, and the nitriding substrate temperature is 400-800 ℃.
Preferably, when the nitriding pressure is less than 15Pa, the nitriding temperature is less than or equal to 550 ℃, and the nitriding time is more than or equal to 3 hours; when the pressure is more than or equal to 15Pa, the nitriding temperature is 550-800 ℃, and the nitriding time is more than or equal to 2 hours.
Preferably, the sputtered metal nitride nanocrystalline coating is titanium nitride, tantalum nitride, or niobium nitride.
Preferably, the sputtering temperature is 200-550 ℃ and the bias voltage is 100-300V during the sputtering process.
Preferably, the metal nitride nanocrystalline coating is sputtered followed by an annealing operation.
Preferably, the annealing temperature is 400-600 ℃ and the annealing time is 1-4h.
Preferably, when the annealing temperature is less than or equal to 500 ℃, the annealing time is more than or equal to 3 hours; and when the annealing temperature is more than 500 ℃, the annealing time is less than 3 hours.
The high-conductivity strong corrosion-resistant coating of the PEM electrolytic cell bipolar plate prepared by any one of the preparation methods comprises a titanium nitride nanocrystalline film and a metal nitride nanocrystalline coating on the surface of the titanium base bipolar plate, wherein the metal nitride nanocrystalline coating is outside the titanium nitride nanocrystalline film; the thickness of the titanium nitride nanocrystalline film is 50-200 nm; the grain size of the metal nitride nanocrystalline coating is 5-40 nm, and the thickness is more than or equal to 100nm.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a high-conductivity strong corrosion-resistant coating of a bipolar plate of a PEM (proton exchange membrane) electrolytic cell, which aims at the surface characteristics of a bipolar plate flow channel of the PEM electrolytic cell and the technical characteristics of magnetron sputtering, firstly, ion nitriding is adopted to carry out surface pretreatment to form a first protection layer which is uniformly distributed, the surface morphology and the structure of a titanium-based bipolar plate are reconstructed, then, the magnetron sputtering technology is adopted to prepare a second protection layer with fine and compact grains, and the problem of poor quality of the PEM electrolytic cell bipolar plate coating prepared by magnetron sputtering is solved. The invention combines the characteristics of high uniformity and compactness of the ion nitriding film, controllable thickness when the magnetron sputtering technology is used for preparing the coating, capability of further optimizing the crystallinity and compactness of the coating and the like through annealing treatment. The nanocrystalline coating prepared by the method has compact structure, prevents corrosive medium from penetrating through the coating to corrode the substrate, has low lattice mismatch degree, improves the binding force between the coating and the substrate, has good conductivity, and further reduces the contact resistance of the bipolar plate.
The plasma nitriding belongs to a chemical gas phase method, has good plating coiling property, has good plating penetrating property for complex surfaces such as a polyhedral structure, a gap, a deep hole and the like, can generate a titanium nitride nanocrystalline structure in situ, realizes the first-stage corrosion-resistant protection for the surface of a base material and the defect, and the titanium nitride nanocrystalline formed by the plasma nitriding provides an effective nucleation site for the preparation of a subsequent magnetron sputtering metal nitride nanocrystalline coating, is favorable for forming a metal nitride second protection layer with fine and compact grains in the magnetron sputtering process, and solves the problem of poor coating quality of a bipolar plate of a PEM (proton exchange membrane) electrolytic cell.
Furthermore, the preparation and heat preservation annealing of the coating are sequentially completed in the cavity of the magnetron sputtering equipment, the problem of oxidation of the coating caused by repeated charging and discharging is avoided, the process is simplified, the growth of crystal grains can be prevented by controlling the temperature, and the binding force of the coating is improved. In addition, the plasma nitriding can sputter and remove oxide on the surface of the base material, so that the production efficiency is improved. The metal nitride coating prepared by the invention avoids the use of noble metals such as Pt, ir and the like, and obviously reduces the cost of the PEM electrolytic tank.
Drawings
FIG. 1 is a graph of the topography of a coating surface of the present invention;
wherein, (a) is a direct magnetron sputtering coating; (b) The figure shows a coating prepared by a composite preparation method
FIG. 2 is a graph of contact resistance of a coating made by various methods in accordance with the present invention;
FIG. 3 is a graph of the corrosion performance of the coatings of the present invention prepared using different methods.
Detailed Description
One of the embodiments of the invention discloses a composite preparation method of a high-conductivity and strong-corrosion-resistance metal nitride coating of a bipolar plate of a PEM (proton exchange membrane) electrolytic cell, which comprises the following steps:
step 1, placing a titanium-based bipolar plate in plasma nitriding equipment, placing the titanium-based bipolar plate on a parallel plate capacitive plasma cathode plate, wherein one side of the side, on which a runner is distributed, faces an anode plate of the parallel plate, and the distance from the anode plate is not more than 100mm, so that nitriding is more uniform due to the anode plate placed in parallel, and nitriding can be performed uniformly at the runner; the bipolar plate is completely wrapped by plasma, and in stable glow plasma, nitrogen element activated by the plasma collides with the surface of the bipolar plate flow channel uniformly, diffuses and reacts to generate titanium nitride.
Specifically, nitriding time is controlled to be 2-6h, nitriding pressure is controlled to be 1-30Pa, nitriding substrate temperature is controlled to be 400-800 ℃, and nanocrystalline with target size can be obtained through nitriding under the temperature, pressure and time; when the nitriding pressure is preferably less than 15Pa, the nitriding temperature is not more than 550 ℃, and the nitriding time is not less than 3 hours; when the pressure is greater than or equal to 15Pa, the nitriding temperature is 550-800 ℃, and the nitriding time is not less than 2 hours; the smaller the pressure is, the better the nitriding effect is, so that the nitriding temperature and the nitriding time are controlled to a certain extent. When the pressure is high, the nitriding effect is general, so that the nitriding temperature and time are improved, and the nitriding effect is ensured.
The voltage between the plasma polar plates of the parallel plate capacitor is 0.8-2KV, the current is 0.2-0.8A, the self-bias voltage is less than 0.8KV (the working voltage and the current of the parallel plate capacitor can be regulated to a certain extent along with the regulation of equipment), the surface of the bipolar plate runner structure is acted by plasma, and a compact titanium nitride nanocrystalline film is formed on the surface of the titanium substrate in situ, wherein the grain size is 5-20 nm, the film thickness is 50-200nm, and the grain orientation is anisotropic. According to the invention, through nitriding, titanium nitride grains can grow in situ, and the generated film has good bonding property with the substrate.
The titanium-based bipolar plate is provided with a runner because the cathode and the anode are respectively provided with a runner, so that after nitriding the anode plate on one side, the titanium-based bipolar plate is turned over, and the process is repeated for the cathode plate on the other layer to carry out nitriding.
And 2, placing the nitrided titanium-based bipolar plate in a magnetron sputtering cavity, controlling the sputtering temperature to be 200-550 ℃, biasing voltage to be 100-300V, sputtering a metal nitride nanocrystalline coating on the surface of titanium nitride formed by plasma nitriding, wherein a coating material system is a corrosion-resistant high-conductivity transition metal nitride, the transition metal nitride is titanium nitride, tantalum nitride or niobium nitride, the thickness of the coating is more than 100nm, the grain size of the coating is 5-40 nm, and the bonding force between the coating prepared by magnetron sputtering and the titanium-based bipolar plate is more than 30N.
And step 3, performing annealing treatment after completing the preparation of the metal nitride coating by adopting magnetron sputtering, wherein the annealing temperature is 400-600 ℃ and the annealing time is 1-4h. The annealing time is not less than 3 hours when the preferable annealing temperature is not higher than 500 ℃; and when the annealing temperature is higher than 500 ℃, the annealing time is less than 3 hours. Through annealing, the two phases at two sides of the interface are mutually diffused, so that the lattice distortion is small, and the binding force of the two phases is improved; annealing also releases and reduces internal stresses between grains. Then, the temperature is reduced along with the furnace, the temperature reduction speed is not higher than 5 ℃/min, and the crystal grains can be slowly diffused by limiting the temperature reduction speed, so that the binding force of the crystal grains is improved. The grain size in the internal titanium nitride film is kept to be smaller than 50nm, and the bonding force between the coating and the bipolar plate substrate is larger than 40N.
Example 1
The titanium base material for the bipolar plate is placed in plasma nitriding equipment, the base material for the bipolar plate is positioned on a parallel plate capacitive plasma cathode plate, the side, on which a runner is distributed, faces an anode plate of the parallel plate, 80mm away from the anode plate, nitriding time is controlled to be 4h, nitriding pressure is controlled to be 10Pa, nitriding base material temperature is controlled to be 500 ℃, voltage between the parallel plate capacitive plasma plates is 0.8KV, current is 0.4A, self-bias voltage is 0.65KV, the base material for the bipolar plate is completely wrapped by plasma, the generated titanium nitride is uniform and compact, grain size of the titanium nitride is about 8nm, and grain orientation anisotropy is achieved. And (3) placing the nitrided bipolar plate substrate in a magnetron sputtering cavity, controlling the sputtering temperature to be 300 ℃, and sputtering the substrate at a bias voltage of 150V on the surface of titanium nitride formed by plasma nitriding to generate a nano titanium nitride coating, wherein the thickness of the coating is 100nm, and the grain size of the coating is about 15nm. The bonding force between the magnetron sputtered coating and the bipolar plate substrate is about 35N. Annealing treatment is carried out after magnetron sputtering is finished, the annealing temperature is controlled to be 420 ℃, the annealing time is controlled to be 3.5 hours, the cooling speed of the furnace is 5 ℃/min, the grain size of the prepared coating is about 20nm, and the coating and the bipolar plate base are preparedThe bonding force of the material is 42N. The contact resistance of the prepared composite coating is 7.5mΩ cm 2 Self-etching current density of 0.93. Mu.A/cm 2 . The method for testing the contact resistance and the self-corrosion current density is adopted by referring to the part 6 of a proton exchange membrane fuel cell of the national standard GBT 20042.6-2011: bipolar plate characteristic test method, binding force test was performed with reference to GBT 30707-2014 "fine ceramic coating binding force test method scratch method", and the methods adopted in the following examples are consistent and will not be described in detail.
The SEM characterization result is shown in fig. 1, the comparative scheme is that the titanium nitride coating prepared by direct magnetron sputtering has spherical crystal grains with the grain size of about 35nm, while the titanium nitride composite coating prepared by the composite preparation method described in example 1 has the crystal grain size obviously reduced and about 20nm, and the surface of the groove-shaped structure on the surface of the substrate is uniformly covered with the coating, so that good coating property and uniformity are shown.
The contact resistance test results of the coating are shown in FIG. 2, in which the contact resistance gradually decreases with increasing contact pressure, and the contact resistance of the commercially pure titanium substrate in the comparative example is about 20mΩ cm under 1.5MPa 2 The contact resistance of the titanium nitride coating prepared by direct magnetron sputtering is about 10mΩ cm 2 Whereas the contact resistance of the titanium nitride composite coating prepared by the composite preparation method described in example 1 was about 7.5mΩ cm 2 The contact resistance is significantly reduced.
The test result of the corrosion performance is shown in FIG. 3, and the adopted corrosion test solution is 0.5mol/L H 2 SO 4 +2ppmF - The test temperature was 80 ℃. The self-etching current density of the commercially pure titanium substrate in the comparative example was about 87. Mu.A/cm 2 The self-etching current density of the titanium nitride coating prepared by direct magnetron sputtering is about 35 mu A/cm 2 Whereas the self-etching current density of the titanium nitride composite coating prepared by the composite preparation method described in example 1 was about 0.93. Mu.A/cm 2 The self-etching current density is significantly reduced.
Example 2
Placing a titanium substrate for a bipolar plate in plasma nitriding equipment, wherein the bipolar plate substrate is positioned in parallel plate capacitor plasmaOn the cathode plate, the side with the flow channels distributed faces the anode plate of the parallel plate, 50mm is far away from the anode plate, nitriding time is controlled to be 4h, nitriding pressure is controlled to be 10Pa, nitriding substrate temperature is 400 ℃, voltage between the parallel plate capacitance plasma plates is 0.8KV, current is 0.6A, self bias is 0.75KV, the bipolar plate substrate is completely wrapped by plasma, generated titanium nitride is uniform and compact, grain size of the titanium nitride is about 5nm, and grain orientation anisotropy is achieved. And (3) placing the nitrided bipolar plate substrate in a magnetron sputtering cavity, controlling the sputtering temperature to be 300 ℃, and sputtering the substrate at a bias voltage of 150V on the surface of titanium nitride formed by plasma nitriding to generate a nano titanium nitride coating, wherein the thickness of the coating is 100nm, and the grain size of the coating is about 10nm. The bonding force of the magnetron sputtered coating to the bipolar plate substrate is about 32N. And (3) performing annealing treatment after the magnetron sputtering is finished, controlling the annealing temperature to 400 ℃, and controlling the annealing time to 4 hours, wherein the cooling speed of the furnace is 5 ℃/min, the grain size of the prepared coating is about 13nm, and the bonding force between the coating and the bipolar plate substrate is 45N. The contact resistance of the prepared composite coating is 6.3mΩ cm 2 Self-etching current density of 0.95. Mu.A/cm 2 。
The contact resistance test results of the coating are shown in FIG. 2, in which the contact resistance gradually decreases with increasing contact pressure, and the contact resistance of the commercially pure titanium substrate in the comparative example is about 20mΩ cm under 1.5MPa 2 The contact resistance of the titanium nitride coating prepared by direct magnetron sputtering is about 10mΩ cm 2 Whereas the contact resistance of the titanium nitride composite coating prepared by the composite preparation method described in example 2 was about 6.3mΩ cm 2 The contact resistance is significantly reduced.
The test result of the corrosion performance is shown in FIG. 3, and the adopted corrosion test solution is 0.5mol/L H 2 SO 4 +2ppmF - The test temperature was 80 ℃. The self-etching current density of the commercially pure titanium substrate in the comparative example was about 87. Mu.A/cm 2 The self-etching current density of the titanium nitride coating prepared by direct magnetron sputtering is about 35 mu A/cm 2 Whereas the self-etching current density of the titanium nitride composite coating prepared by the composite preparation method described in example 2 was about 0.95. Mu.A/cm 2 The self-etching current density is significantly reduced.
Example 3
The titanium base material for the bipolar plate is placed in plasma nitriding equipment, the base material for the bipolar plate is positioned on a parallel plate capacitive plasma cathode plate, the side, on which the flow channels are distributed, faces the parallel plate anode plate, is 100mm away from the anode plate, nitriding time is controlled to be 3h, nitriding pressure is 15Pa, nitriding base material temperature is 650 ℃, voltage between the parallel plate capacitive plasma plates is 1KV, current is 0.8A, self-bias voltage is 0.7KV, the base material for the bipolar plate is completely wrapped by plasma, titanium nitride is uniform and compact, grain size of the titanium nitride is about 5nm, and grain orientation anisotropy is achieved. And (3) placing the nitrided bipolar plate substrate in a magnetron sputtering cavity, controlling the sputtering temperature to be 200 ℃, controlling the bias voltage to be 200V, and sputtering the surface of titanium nitride formed by plasma nitriding to generate a nano niobium nitride coating, wherein the thickness of the coating is 150nm, and the grain size of the coating is about 8nm. The bonding force of the magnetron sputtered coating to the bipolar plate substrate is about 32N. And (3) performing annealing treatment after the magnetron sputtering is finished, controlling the annealing temperature to be 500 ℃, and controlling the annealing time to be 3 hours, wherein the cooling speed of the furnace is 5 ℃/min, the grain size of the prepared coating is about 18nm, and the bonding force between the coating and the bipolar plate substrate is 32N. The contact resistance of the prepared composite coating is 4.3mΩ cm 2 Self-etching current density of 0.77. Mu.A/cm 2 。
Example 4
The titanium base material for the bipolar plate is placed in plasma nitriding equipment, the base material for the bipolar plate is positioned on a parallel plate capacitive plasma cathode plate, the side, on which the flow channels are distributed, faces an anode plate of the parallel plate, is 100mm away from the anode plate, nitriding time is controlled to be 5h, nitriding pressure is 15Pa, nitriding base material temperature is 650 ℃, voltage between the parallel plate capacitive plasma plates is 1.2KV, current is 0.8A, self-bias voltage is 0.7KV, the base material for the bipolar plate is completely wrapped by plasma, the generated titanium nitride is uniform and compact, grain size of the titanium nitride is about 15nm, and grain orientation anisotropy is achieved. And (3) placing the nitrided bipolar plate substrate in a magnetron sputtering cavity, controlling the sputtering temperature to be 300 ℃, and sputtering the substrate at a bias voltage of 150V on the surface of titanium nitride formed by plasma nitriding to generate a nano niobium nitride coating, wherein the thickness of the coating is 150nm, and the grain size of the coating is about 20nm. The bonding force of the magnetron sputtered coating to the bipolar plate substrate is about 32N. Annealing treatment is carried out after magnetron sputtering is completed, and annealing is controlledThe temperature of the fire is 600 ℃, the annealing time is 2.5 hours, the cooling speed of the furnace is 5 ℃/min, the grain size of the prepared coating is about 23nm, and the binding force between the coating and the bipolar plate substrate is 38N. The contact resistance of the prepared composite coating is 3.2mΩ cm 2 Self-etching current density of 0.86. Mu.A/cm 2 。
Example 5
The titanium base material for the bipolar plate is placed in plasma nitriding equipment, the base material for the bipolar plate is positioned on a parallel plate capacitive plasma cathode plate, the side, on which a runner is distributed, faces an anode plate of the parallel plate, is 30mm away from the anode plate, nitriding time is controlled to be 2h, nitriding pressure is controlled to be 20Pa, nitriding base material temperature is controlled to be 650 ℃, voltage between the parallel plate capacitive plasma plates is 0.8KV, current is 0.55A, self-bias voltage is 0.8KV, the base material for the bipolar plate is completely wrapped by plasma, the generated titanium nitride is uniform and compact, grain size of the titanium nitride is about 18nm, and grain orientation anisotropy is achieved. And (3) placing the nitrided bipolar plate substrate in a magnetron sputtering cavity, controlling the sputtering temperature to be 550 ℃, and sputtering the substrate at a bias voltage of 100V on the surface of titanium nitride formed by plasma nitriding to generate a nano tantalum nitride coating, wherein the thickness of the coating is 300nm, and the grain size of the coating is about 30nm. The bonding force of the magnetron sputtered coating to the bipolar plate substrate is about 32N. And (3) performing annealing treatment after the magnetron sputtering is finished, controlling the annealing temperature to 550 ℃, and controlling the annealing time to 1h, wherein the cooling speed of the furnace is 5 ℃/min, the grain size of the prepared coating is about 32nm, and the bonding force between the coating and the bipolar plate substrate is 32N. The contact resistance of the prepared composite coating is 4.3mΩ cm 2 Self-etching current density of 0.77. Mu.A/cm 2 。
Example 6
The titanium base material for the bipolar plate is placed in plasma nitriding equipment, the base material for the bipolar plate is positioned on a parallel plate capacitive plasma cathode plate, the side, on which a runner is distributed, faces an anode plate of the parallel plate, is 30mm away from the anode plate, nitriding time is controlled to be 6h, nitriding pressure is controlled to be 30Pa, nitriding base material temperature is controlled to be 800 ℃, voltage between the parallel plate capacitive plasma plates is 1.2KV, current is 0.65A, self-bias voltage is 0.6KV, the base material for the bipolar plate is completely wrapped by plasma, the generated titanium nitride is uniform and compact, grain size of the titanium nitride is about 20nm, and grain orientation anisotropy is achieved. Placing the nitrided bipolar plate base material in a magnetIn the sputtering cavity, the sputtering temperature is controlled to be 200 ℃, the bias voltage is controlled to be 300V, a nano tantalum nitride coating is generated on the surface of titanium nitride formed by plasma nitriding in a sputtering mode, the thickness of the coating is 200nm, and the grain size of the coating is about 35nm. The bonding force of the magnetron sputtered coating to the bipolar plate substrate is about 32N. And (3) performing annealing treatment after the magnetron sputtering is finished, controlling the annealing temperature to be 600 ℃, and controlling the annealing time to be 2.5 hours, wherein the cooling speed of the furnace is 5 ℃/min, the grain size of the prepared coating is about 40nm, and the bonding force between the coating and the bipolar plate substrate is 47N. The contact resistance of the prepared composite coating is 7.6mΩ cm 2 Self-etching current density of 1.09. Mu.A/cm 2 。
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a high-conductivity strong corrosion-resistant coating of a bipolar plate of a PEM electrolytic cell is characterized in that a titanium nitride nanocrystalline film is prepared on the surface of a titanium-based bipolar plate through nitriding; sputtering a metal nitride nanocrystalline coating on the surface of the titanium nitride nanocrystalline film, wherein the metal nitride nanocrystalline is a transition metal nitride nanocrystalline; preparing a high-conductivity strong corrosion-resistant coating on the surface of the titanium-based bipolar plate;
the grain size of the titanium nitride nanocrystalline film is 5-20 nm; the grain size of the metal nitride nanocrystalline coating is 5-40 nm.
2. The method for preparing the high-conductivity and high-corrosion-resistance coating for the bipolar plate of the PEM electrolytic tank, according to claim 1, wherein in the nitriding process, the side with the runner is faced to the anode plate, and the distance between the side with the runner and the anode plate is less than or equal to 100mm.
3. The method for preparing the high-conductivity and strong-corrosion-resistance coating for the bipolar plate of the PEM electrolytic tank, which is disclosed in claim 1, is characterized in that nitriding time is 2-6h, nitriding pressure is 1-30Pa, and nitriding substrate temperature is 400-800 ℃.
4. The method for preparing the high-conductivity and high-corrosion-resistance coating for the bipolar plate of the PEM electrolytic tank according to claim 3, wherein when the nitriding pressure is less than 15Pa, the nitriding temperature is less than or equal to 550 ℃, and the nitriding time is more than or equal to 3 hours; when the pressure is more than or equal to 15Pa, the nitriding temperature is 550-800 ℃, and the nitriding time is more than or equal to 2 hours.
5. The method for preparing the high-conductivity and high-corrosion-resistance coating for the bipolar plate of the PEM electrolytic cell according to claim 1, wherein the sputtered metal nitride nanocrystalline coating is titanium nitride, tantalum nitride or niobium nitride.
6. The method for preparing a highly conductive and highly corrosion resistant coating for a bipolar plate of a PEM electrolyzer of claim 1 wherein the sputtering temperature is 200-550 ℃ and the bias voltage is 100-300V during the sputtering process.
7. The method for preparing a highly conductive and highly corrosion resistant coating for a bipolar plate of a PEM electrolyser in accordance with any one of claims 1-6 wherein the metal nitride nanocrystalline coating is sputtered followed by an annealing operation.
8. The method for preparing a high conductivity and corrosion resistant coating for bipolar plates of PEM electrolytic cells according to claim 7, wherein the annealing temperature is 400-600 ℃ and the annealing time is 1-4 hours.
9. The method for preparing the high-conductivity and high-corrosion-resistance coating for the bipolar plate of the PEM electrolytic tank, which is characterized in that when the annealing temperature is less than or equal to 500 ℃, the annealing time is more than or equal to 3 hours; and when the annealing temperature is more than 500 ℃, the annealing time is less than 3 hours.
10. A PEM electrolyser bipolar plate high conductivity strong corrosion resistant coating prepared by the method of any one of claims 1-9, characterized in that it comprises a titanium nitride nanocrystalline film and a metal nitride nanocrystalline coating on the surface of the titanium base bipolar plate, the metal nitride nanocrystalline coating being outside the titanium nitride nanocrystalline film; the thickness of the titanium nitride nanocrystalline film is 50-200 nm; the grain size of the metal nitride nanocrystalline coating is 5-40 nm, and the thickness is more than or equal to 100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311345827.1A CN117305878A (en) | 2023-10-17 | 2023-10-17 | High-conductivity strong corrosion-resistant coating for bipolar plate of PEM (PEM) electrolytic tank and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311345827.1A CN117305878A (en) | 2023-10-17 | 2023-10-17 | High-conductivity strong corrosion-resistant coating for bipolar plate of PEM (PEM) electrolytic tank and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117305878A true CN117305878A (en) | 2023-12-29 |
Family
ID=89288206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311345827.1A Pending CN117305878A (en) | 2023-10-17 | 2023-10-17 | High-conductivity strong corrosion-resistant coating for bipolar plate of PEM (PEM) electrolytic tank and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117305878A (en) |
-
2023
- 2023-10-17 CN CN202311345827.1A patent/CN117305878A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11799094B2 (en) | Graphite micro-crystalline carbon coating for metal bipolar plates of fuel cells and application thereof | |
| CN110684946B (en) | Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof | |
| WO2019144853A1 (en) | Corrosion-resistant conductive film, and pulsed bias voltage alternate magnetron sputtering deposition method and application thereof | |
| CN104766980B (en) | Acid medium flue cell bipolar plate protection coating and preparing method thereof | |
| CN110137525A (en) | A kind of fuel battery metal double polar plate coating and technology of preparing | |
| WO2023284596A1 (en) | High-conductivity, corrosion-resistant and long-lifetime max phase solid solution composite coating, and preparation method therefor and use thereof | |
| CN113235062B (en) | MAX-phase multilayer composite coating and preparation method and application thereof | |
| CN113584441B (en) | Metal bipolar plate coating and preparation method thereof | |
| CN114597436B (en) | Protective coating for metal bipolar plate and preparation method thereof | |
| CN114481048B (en) | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating and preparation method and application thereof | |
| CN107195909A (en) | A kind of preparation method of fuel battery double plates and its surface titanium film | |
| CN114231925A (en) | Fuel cell metal bipolar plate composite coating and preparation method thereof | |
| CN112820890B (en) | Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate | |
| CN114464818A (en) | Low-cost surface treatment method for improving surface performance of titanium and titanium alloy for proton exchange membrane fuel cell polar plate | |
| CN110265668B (en) | Metal bipolar plate of hydrogen fuel cell and preparation method thereof | |
| CN117305878A (en) | High-conductivity strong corrosion-resistant coating for bipolar plate of PEM (PEM) electrolytic tank and preparation method thereof | |
| CN110880608A (en) | Metal bipolar plate composite film layer for hydrogen fuel cell and preparation method thereof | |
| CN113328111B (en) | Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof | |
| CN115411285A (en) | Fuel cell bipolar plate containing anticorrosive film and preparation method thereof | |
| CN115029663A (en) | Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell | |
| CN115207388A (en) | High-ductility precoating nanocrystalline gradient sheet for fuel cell metal polar plate and preparation thereof | |
| CN112993299B (en) | Silicon-doped niobium carbide coating of metal bipolar plate of fuel cell and preparation method thereof | |
| CN109735869B (en) | Corrosion-resistant conductive alloy film layer and preparation method and application thereof | |
| CN206878105U (en) | A kind of fuel battery double plates | |
| CN115832336B (en) | Fuel cell metal polar plate precoat and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |