CN117867412A - High corrosion resistance stainless steel for fuel cell bipolar plate - Google Patents
High corrosion resistance stainless steel for fuel cell bipolar plate Download PDFInfo
- Publication number
- CN117867412A CN117867412A CN202410262926.1A CN202410262926A CN117867412A CN 117867412 A CN117867412 A CN 117867412A CN 202410262926 A CN202410262926 A CN 202410262926A CN 117867412 A CN117867412 A CN 117867412A
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- fuel cell
- corrosion resistance
- equal
- bipolar plate
- 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.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 123
- 230000007797 corrosion Effects 0.000 title claims abstract description 106
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 87
- 239000010935 stainless steel Substances 0.000 title claims abstract description 82
- 239000000446 fuel Substances 0.000 title claims abstract description 62
- 210000004027 cell Anatomy 0.000 abstract description 50
- 229910052721 tungsten Inorganic materials 0.000 abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 239000012528 membrane Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- 210000000170 cell membrane Anatomy 0.000 abstract description 2
- 230000002939 deleterious effect Effects 0.000 abstract 1
- 238000004088 simulation Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 230000002829 reductive effect Effects 0.000 description 18
- 238000002161 passivation Methods 0.000 description 15
- 238000005242 forging Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000010287 polarization Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000005098 hot rolling Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 238000005266 casting Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 229910001566 austenite Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000001914 calming effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical class [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Fuel Cell (AREA)
Abstract
The invention belongs to the technical field of stainless steel, and discloses a high corrosion resistance stainless steel for a fuel cell bipolar plate. Adopts a high Cr low Ni element content system, adopts W, cu part to replace Mo to obtain the high corrosion resistance stainless steel, and simultaneously reduces the addition of noble elements Ni and Mo. The corrosion current density of the high corrosion resistance stainless steel of the bipolar plate of the fuel cell meets the technical requirements of DOE2025 of the United states department of energy under the long-time simulation of the cathode and anode operation environment of the fuel cell, and the corrosion resistance is better. The low corrosion current density indicates less metal ions are released due to dissolution in the operating environment, reducing the deleterious effects of metal ions on the fuel cell membrane electrode and proton exchange membrane.
Description
Technical Field
The invention relates to the technical field of stainless steel, in particular to a high corrosion resistance stainless steel for a fuel cell bipolar plate.
Background
Stainless steel has excellent mechanical and corrosion resistance, and is widely applied to the fields of energy, electric power, chemical industry and the like, and manufacturing materials of bipolar plates for proton exchange membrane fuel cells. The corrosion-resistant mechanism of stainless steel is that elements such as Cr on the surface of the stainless steel and oxygen in the air form a layer of extremely thin, compact and well-adhesive passivation film which is used as a protective barrier to isolate a corrosion medium from a substrate; although the metal under the protection of the passivation film still has certain reaction capability, the passivation film has good self-repairing function. However, the fuel cell has a complex operating environment, and it is difficult to ensure the integrity of the passivation film under certain conditions, such as erosion of fluorine ions at high temperature (about 70 ℃), and corrosion may occur. The current stainless steel has poor corrosion resistance under the working condition of a proton exchange membrane fuel cell, and is easy to corrode and dissolve out metal ions to pollute an electrolyte membrane and generate a passivation film to increase contact resistance, so that the metal bipolar plate is required to be subjected to surface corrosion prevention and conductive treatment. The existing surface modification method is to prepare a corrosion-resistant and conductive coating on the surface of metal, but the surface coating is difficult to avoid local defects, the area has weak protection capability, and the base metal is difficult to protect in the high-temperature strong oxidizing and strong acid solution of the fuel cell, so that the base metal is corroded and dissolved, and the operation and the safety of the fuel cell are seriously affected. Thus, even coated metal substrates require high corrosion resistance requirements.
The current stainless steel bipolar plate material mainly adopts 316L, has good bipolar plate runner forming capability, but the corrosion resistance of the stainless steel bipolar plate material cannot meet the requirements of the American DOE2025 standard under the working environment of a fuel cell, and has higher manufacturing cost due to the addition of Mo and Ni elements, and has larger limit on the further commercial application and low-cost preparation of the stainless steel bipolar plate. Therefore, it is necessary to develop a novel composition stainless steel, which can reduce the addition amount of noble elements to reduce the cost of stainless steel materials under the condition of fully meeting the corrosion resistance requirement of the fuel cell operating environment.
Disclosure of Invention
The technical problem to be solved by the invention is to solve the problems that the stainless steel for the bipolar plate which meets the corrosion resistance requirement of the fuel cell is not available in China at present and the cost is high due to the addition of Mo and Ni elements of austenitic stainless steel, and the equivalent Cr is controlled by increasing the Cr content, reducing the Ni content E Equivalent Ni E Is a ratio of (2); w, cu is added to replace Mo element partially, nb and Ti are further added to reduce the content of harmful elements C, N to corrosion resistance in the stainless steel, improve the corrosion resistance of the stainless steel in the working environment of the fuel cell, reduce the corrosion current density of the stainless steel in the environment simulating the anode and cathode of the fuel cell, improve the self-corrosion potential, reduce the addition of noble elements Mo and Ni and reduce the preparation cost of bipolar plate materials.
The technical scheme of the invention is as follows: the high corrosion resistance stainless steel of the bipolar plate of the fuel cell comprises the following elements in percentage by mass: c is less than or equal to 0.01, cr is less than or equal to 25-35, ni is less than or equal to 0.5-4, si is less than or equal to 1, mn is less than or equal to 5.0, cu is less than or equal to 0.2-2.0, mo is less than or equal to 2-5.0, W is less than or equal to 0.1-1.5, N is less than or equal to 0.01, P is less than or equal to 0.02, S is less than or equal to 0.01, O is less than or equal to 0.001, and the mass percentages of Nb elements are: nb is more than or equal to 7.75×C+0.2, and Ti element is more than or equal to 3.43×N and less than or equal to 7.75×C+0.23.43 XN+0.03, the balance being Fe; wherein Cr is E /Ni E More than or equal to 5.5, the Cr E Cr is the sum of the following element mass percent relation E =cr+mo+1.5si+0.5nb, the Ni E Ni is the sum of the following mass percent relation of each element E =Ni+30(C+N)+0.5Mn+0.25Cu。
The fuel cell bipolar plate high corrosion resistance stainless steel Cr element comprises the following components in percentage by mass: cr=27 to 29.
The fuel cell bipolar plate high corrosion resistance stainless steel comprises the following Ni elements in percentage by mass: ni=2 to 4.
The high corrosion resistance stainless steel W element of the bipolar plate of the fuel cell comprises the following components in percentage by mass: w=0.2-0.6, the mass percentage of the Mo element of the stainless steel with high corrosion resistance of the fuel cell bipolar plate is as follows: mo=2 to 4.0.
A high corrosion resistance stainless steel for fuel cell bipolar plate adopts a high Cr low Ni content system, adopts W, cu part to replace Mo, reduces the addition of noble elements Ni and Mo, and controls the content of C, N in the stainless steel below 0.01.
Cr is a ferrite forming element, can obviously improve the corrosion resistance of stainless steel, but the excessive addition can lead to Cr-rich sigma and Laves phases in the heat treatment cooling process, which not only seriously reduces the corrosion resistance of a matrix, but also worsens the mechanical property, so that the fuel cell bipolar plate high corrosion resistance stainless steel comprises the following Cr elements in percentage by mass: 25-35; preferably, the mass percentage of Cr element is as follows: 27-29.
The Ni element is an austenite forming element which improves the passivation ability of stainless steel in a strong corrosive medium and thus improves corrosion resistance, and has a strong effect of promoting austenite formation, but an excessively high Ni content in ferritic stainless steel leads to easy precipitation of an austenite phase during heat treatment and thus decreases corrosion resistance and mechanical properties of the inventive steel, and fig. 1 is a phase diagram of example 3, in which when the Cr content is 4%, the austenite phase precipitation temperature is lower than the Sigma (Sigma) phase precipitation temperature, and the austenite phase content precipitated during subsequent rolling annealing is less. Content of Austenitic precipitated phase in ferritic stainless steel and Cr equivalent Cr E =cr+mo+1.5si+0.5nb andni equivalent Ni E Regarding the ratio of=ni+30 (c+n) +0.5mn+0.25cu, cr in example 3 of the present invention E /Ni E The austenitic stainless steel is more than or equal to 5.5, the austenitic phase precipitation temperature is less than the Sigma (Sigma) phase precipitation temperature, the austenitic phase content can be reduced after heat treatment, the corrosion resistance and the processing forming ability of the stainless steel are considered in the use process, and the high corrosion resistance stainless steel Ni element of the fuel cell bipolar plate comprises the following components in percentage by mass: 0.5-4; preferably, the mass percentage of the Ni element is as follows: 2-4.
The W element is an element for enhancing the corrosion resistance of the stainless steel, and the W has the advantages of high melting point, large density, high hardness and the like, and is a more emerging stainless steel alloy element. W is a ferrite forming element which is the same group as Mo in the periodic Table of elements, and is a group VIB element, both of which are dissolved in an etching solution to form WO 4 2- With MoO 4 2- It reacts with other metal cations on the surface of the passivation film to form complex precipitates insoluble in water, which adsorb at the stainless steel/passivation film interface, thereby inhibiting dissolution of the metal matrix, and which also react with aggressive ions such as F - 、SO 4 2- Etc. to reduce F - 、SO 4 2- The concentration further weakens the damage effect on the passive film, and the effect of the W element is more obvious due to the fact that the number of the out-of-core electron layers is more, so that the corrosion resistance is more influenced, and the corrosion resistance of the stainless steel can be obviously improved when the addition amount of the W element is smaller. However, excessive W addition promotes sigma phase formation in the stainless steel, and not only reduces the corrosion resistance of the stainless steel, but also deteriorates the mechanical property, so that the high corrosion resistance stainless steel of the fuel cell bipolar plate comprises the following W elements in percentage by mass: 0.1 to 1.5, preferably, the mass percentage of W element is W=0.2 to 0.6;
mo is a ferrite forming element, and the synergistic effect of the Mo and Cr in stainless steel can obviously improve the pitting corrosion resistance of the stainless steel, but the excessive addition can lead to precipitation of Laves intermetallic compounds, reduce the plastic forming capability of the stainless steel, and the Mo element is more expensive, and the mass percent of the Mo element of the high corrosion resistance stainless steel of the fuel cell bipolar plate is as follows in consideration of cost: mo=2 to 5.0, preferably mo=2 to 4.0.
Cu is an austenite forming element, can obviously improve the corrosion resistance of stainless steel in reducing acid, has strong solid solution and precipitation strengthening effects, and takes the subsequent processing and forming capabilities of the stainless steel into consideration, the fuel cell bipolar plate high corrosion resistance stainless steel comprises the following Cu elements in percentage by mass: 0.2-2.
The maximum solid solubility of C and N elements in ferrite is generally lower than 0.004% and 0.006%, respectively, and when the content of C and N elements in ferrite stainless steel is too high, carbide (Cr, fe) is formed by combining with Cr 23 C 6 And (Cr, fe) 7 C 3 Nitrides CrN and Cr 2 N, causes partial chromium deficiency to significantly deteriorate the corrosion resistance of the ferritic stainless steel. The upper limit of the C and N contents in the ferritic stainless steel in the present invention is 0.01%.
The Nb and Ti elements can be combined with the C and N elements in the ferritic stainless steel to form NbC and TiN, and a small amount of Nb and Ti elements are added into the stainless steel in order to further reduce the content of the C and N elements in the matrix. Nb is 92.9 in atomic weight, C is 12 in atomic weight, the ratio of Nb to C is 7.75 in atomic weight, ti is 47.9 in atomic weight, and N is 14 in atomic weight, the ratio of Ti to N is 3.43 in atomic weight, based on the respective elemental composition in the present invention, the Nb and Ti contents satisfy 7.75XC.ltoreq.Nb.ltoreq.75XC+0.2 and 3.43XN.ltoreq.Ti.ltoreq.3.43XN+0.03, respectively, and the surplus Nb and Ti are dissolved in the matrix to form a solid solution, have weak strengthening and toughening effects, but the excessive addition of Nb and Ti causes deterioration of the formability, so that the addition amount thereof is strictly controlled within the above range.
The alloy is prepared in the component range of the stainless steel, the content of main elements such as Cr, ni, W, cu in the alloy is controlled according to the performance requirement, and the raw materials of each component are high-purity raw materials, so that the content of nonmetallic and metallic impurities is extremely low, and the purity of impurity elements such as C, H, O, P, S and the like through the raw materials is ensured.
Compared with Mo element, cr, W and Cu elements have more remarkable effect in improving the corrosion resistance of the stainless steel in the fuel cell operating environment, and even if the addition amount is smaller, the remarkable effect can be achieved. Therefore, W, cu is adopted to replace part of Mo, so that the content of Cr element is increased, the addition amount of Mo element is reduced, and the cost of the stainless steel material is reduced on the premise of improving the corrosion resistance.
Compared with the prior art, the invention has the beneficial effects that: the current stainless steel for the bipolar plate cannot meet the corrosion resistance requirement under the working environment of the fuel cell, and the problem of higher cost caused by adding Mo and Ni elements is solved, the Cr content is increased, the Ni content is reduced, W, cu is added to partially replace the Mo element, the corrosion resistance of the stainless steel under the working environment of the fuel cell is improved, the corrosion current density of the stainless steel under the working potential of a cathode and an anode of the simulated fuel cell is reduced, the addition of noble elements Mo and Ni is reduced, and the preparation cost of bipolar plate materials is reduced.
Drawings
FIG. 1 is a phase diagram of JMatPro calculation example 3;
FIG. 2 is a chart of example 3 at 70℃and 0.5MH 2 SO 4 +2ppmF - Simulating electrokinetic potential polarization curves of a cathode (air-in) and an anode (hydrogen-in) of the fuel cell in the solution;
FIG. 3 is a chart of example 3 at 70℃and 0.5MH 2 SO 4 +2ppmF - In-solution simulated fuel cell cathode (0.23V) VS. MSE, ventilation) and anode (-0.47V) VS. MSE, hydrogen gas) environment.
Detailed Description
The various smelting and casting processes of the present invention are not limited by the examples below, and any modifications and variations within the scope of the invention as claimed are within the scope of the invention. The following describes embodiments of the present invention in detail with reference to examples and drawings, thereby verifying the advantageous effects of the present invention.
The invention aims to provide a high corrosion resistance stainless steel for a fuel cell bipolar plate and a preparation method thereof. The technical proposal adopted by the invention for solving the technical problems is that the high corrosion resistance stainless steel of the bipolar plate of the fuel cell ensures Cr by increasing the Cr content and reducing the Ni content E /Ni E The stainless steel is reduced more than or equal to 5.5, W, cu is added to partially replace Mo element, and the working environment of the stainless steel in the fuel cell is improvedThe corrosion resistance of the bipolar plate material is reduced, the corrosion current density of the bipolar plate material in the environment simulating the anode and cathode of the fuel cell is reduced, the addition of noble elements Mo and Ni is reduced, and the preparation cost of the bipolar plate material is reduced. The stainless steel comprises the following elements in percentage by mass: c is less than or equal to 0.01, cr is less than or equal to 25-35, ni is less than or equal to 0.5-4, si is less than or equal to 1, mn is less than or equal to 5.0, cu is less than or equal to 0.2-2.0, mo is less than or equal to 2-5.0, W is less than or equal to 0.1-1.5, nb is less than or equal to 7.75 xC+ 0.2,3.43 xN is less than or equal to 3.43 xN+0.03, N is less than or equal to 0.01, P is less than or equal to 0.02, S is less than or equal to 0.01, O is less than or equal to 0.001, and the balance is Fe.
A preparation method of high corrosion resistance stainless steel for a fuel cell bipolar plate comprises the following steps:
(1) Smelting and casting;
according to the mass percentage of each element, arc melting or induction melting is adopted to obtain molten steel, and alloy cast ingots are cast; because the alloy has high requirements on inclusions, the method for producing stainless steel by adopting a converter vacuum oxygen blowing decarburization method and other industrial production methods is not suitable, and the alloy can be prepared by adopting an arc melting or induction melting method. Vacuum or argon protection is adopted during smelting, so that the oxidation burning loss of alloy elements is avoided.
(2) Performing hot deformation cogging processing on the cast ingot;
forging and hot rolling in sequence;
heating the alloy cast ingot to 1150-1250 ℃ in a specific forging process, preserving heat for 3-5 hours, discharging from a furnace for forging, wherein the initial forging temperature is 1100-1200 ℃, the final forging temperature is more than or equal to 1000 ℃, the forging ratio is more than or equal to 3.0, the extension ratio is more than or equal to 2.0, and the sum of the forging ratio and the extension ratio is more than or equal to 5.0;
the specific hot rolling process is that the forged alloy cast ingot is heated to 1100 ℃ to 1250 ℃, is kept for 3 to 5 hours and then is discharged for rolling, the initial rolling temperature of hot rolling is 1100 ℃ to 1200 ℃, the final rolling temperature is more than or equal to 1000 ℃, and the total hot rolling yield of the plate is more than or equal to 90%;
(3) Performing high-temperature heat treatment;
after hot rolling, annealing treatment is carried out at 950-1050 ℃, the heat preservation time is 10-120 minutes, and vacuum or gas protection is adopted during heating; after annealing, water, oil, argon, nitrogen or helium are adopted for rapid cooling; the aim of high temperature heat preservation and rapid cooling is to make corrosion resistant alloy elements Cr, W, mo and the like fully solid-solved, and to obtain nearly equiaxial ferrite grain structure without intermetallic precipitated phase, thereby reducing corrosion resistant element segregation and precipitation and reducing grain boundary corrosion tendency.
(4) Cold deformation;
the cooled sheet material is subjected to cold deformation by adopting cold rolling or deep cold rolling to obtain the size and specification required by the product, and the total deformation of the cold deformation is not less than 80 percent according to the reduction rate.
The temperature of a melting pool for arc melting or induction melting is 1680-1720 ℃; and (3) calming for 5-10 minutes before casting, and casting molten steel under vacuum or argon protection at 1500-1600 ℃.
And (3) performing high-temperature heat treatment, namely performing vacuum heating-gas quenching, continuous heating-water cooling quenching, continuous heating-high-pressure gas quenching, gas protection heating-water quenching or gas protection heating-oil quenching.
After alloy smelting and casting, high temperature forging and hot rolling thinning, heating to above 1000 deg.c to make Cr, W, mo, etc. as anticorrosive alloy elements form solid solution, cooling to room temperature to obtain near equiaxial ferrite grain structure without intermetallic precipitate phase and thus high anticorrosive performance.
The fuel cell bipolar plate low-cost high-corrosion-resistance stainless steel subjected to the high-temperature heat treatment is subjected to electrochemical test for simulating the working condition of the fuel cell, and contains 2ppmF - 0.5mol/L H 2 SO 4 Heating the aqueous solution to 70 ℃ by using a water bath box, and continuously introducing air or hydrogen into the electrolyte at a flow rate of 20 ml/min; first, the working electrode was subjected to potential polarization at-1.37vvs.mse for 5min to remove native oxide films formed in the atmosphere, and all electrochemical measurements were performed when the open circuit potential OCP reached a steady state value. Potentiodynamic polarization scanning is carried out at a scanning rate of 2 mV/s; and (3) performing potentiostatic polarization in an environment of oxygen ventilation near 0.23Vvs. MSE and hydrogen ventilation near-0.47 Vvs. MSE, and measuring the change of corrosion current along with polarization time, wherein the polarization time is 4h. The self-corrosion current and the self-corrosion potential are obtained by adopting Tafel (Tafel) extrapolation method and are used as the basis for comparing the corrosion resistance of the alloy.
Examples
Selecting high-purity iron rods, metal chromium particles, electrolytic nickel plates, ferrotungsten and high-purity silicon particles, and adopting vacuum or argon protection during smelting to refine the stainless steel within the composition range, wherein the mass percentages of the elements are as follows:
example 1: c=0.01, cr=25, ni=4, si=0.8, mn=3.2, cu=0.7, mo=4, w=0.6, nb=0.22, ti=0.04, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =4.8；
Example 2: c=0.01, cr=27, ni=4, si=0.8, mn=3.2, cu=0.7, mo=4, w=0.6, nb=0.22, ti=0.04, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =5.1；
Example 3: c=0.01, cr=29, ni=4, si=0.8, mn=2.9, cu=0.7, mo=4, w=0.6, nb=0.22, ti=0.04, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =5.5；
Example 4: c=0.01, cr=35, ni=2, si=1, mn=5.0, cu=2, mo= 5,W =1.5, nb=0.2775, ti=0.0643, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =7.4；
Example 5: c=0.01, cr=35, ni=4, si=1, mn=3.2, cu=0.7, mo= 5,W =1.5, nb=0.2775, ti=0.0643, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =6.5；
Example 6: c=0.01, cr=29, ni=0.5, si=0.8, mn=3.2, cu=0.2, mo=2, w=0.1, nb=0.0775, ti=0.0343, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =11.7；
Example 7: c=0.01, cr=29, ni=2, si=0.8, mn=3.2, cu=0.7, mo=4, w=0.6, nb=0.22, ti=0.04, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =7.8；
Example 8: c=0.01, cr=29, ni=4, si=0.8, mn=2.9, cu=0.7, mo=4, w=0.2, nb=0.22, ti=0.04, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =5.5；
Example 9: c=0.01, cr=29, ni=3, si=0.8, mn=3.2, cu=0.7, mo=32, w=0.6, nb=1, ti=0.04, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =6.3；
Example 10: c=0.01, cr=29, ni=3, si=0.8, mn=3.2, cu=0.7, mo=3.2, w=0.6, nb=0.22, ti=0.1, n=0.01, p=0.02, s=0.01, o=0.001, the balance being Fe; cr (Cr) E /Ni E =6.2。
All the embodiment steels are cast into alloy cast ingots through arc melting or induction melting; smelting is carried out in vacuum or argon protection, and a stirring technology is utilized to uniformly mix the metal solution in the smelting process; casting under vacuum or argon protection to obtain square or round ingot;
heating a casting blank to 1200 ℃, preserving heat for 3 hours, and then discharging the casting blank from a furnace to forge the casting blank into a forging blank with the size of 100 multiplied by 60 multiplied by 45mm, wherein the initial forging temperature is 1200 ℃, the final forging temperature is 1100 ℃, the forging ratio is 3.0, the extension ratio is 2.0, and the total ratio of the forging ratio to the extension ratio is 5.0;
heating the forging stock to 1200 ℃, preserving heat for 4 hours, performing hot rolling and thinning to 4mm, wherein the initial rolling temperature of hot rolling is 1200 ℃, the final rolling temperature is 1050 ℃, the total hot rolling yield of the plate is 90%, and cooling to room temperature after hot rolling is completed;
the hot rolled plate is quenched after solution treatment at 1050 ℃, the heat preservation time is 30min, no protective gas is needed during heating, and water cooling to room temperature is finished after heat preservation.
The method for testing the corrosion resistance in the embodiment of the invention comprises the steps of processing a solution-treated hot rolled plate into a 10mm multiplied by 2mm sample, polishing the back surface to be smooth, connecting the surface with copper wires, ensuring that the surface to be tested is exposed after the surface is conducted and packaged with denture base resin, polishing the surface to be tested with 240 # abrasive paper, 400 # abrasive paper, 600 # abrasive paper, 800 # abrasive paper, 1000 # abrasive paper and 1500# abrasive paper in sequence, cleaning the surface with deionized water and alcohol, and drying the surface. The electrolyte is in the range of 2ppmF - 0.5mol/L H 2 SO 4 The aqueous solution was heated to 70℃in a water bath, and air or hydrogen was continuously introduced throughout the experiment at a flow rate of 20ml/min. The electrochemical test is carried out by adopting a CS2350M electrochemical workstation, a three-electrode system is adopted, high corrosion resistant stainless steel is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated Mercurous Sulfate Electrode (MSE) is used as a reference electrode. By a means ofAll experiments were performed 3 times.
Self-corrosion current density I of example steels by Tafel extrapolation of polarization curves corr And self-corrosion potential E corr The self-corrosion potential represents the thermodynamic behavior of the metal in the corrosive environment, i.e., how hard the corrosion occurs, while the self-corrosion current density represents the kinetic behavior of the metal in the corrosive environment, i.e., how fast the corrosion proceeds after the corrosion occurs. As shown in table 1, the corrosion resistance and Cr content of the examples directly correlate in the cathode (vented) and anode (vented) operating environments of the fuel cell, and as the Cr content increases from 25% to 35%, the corrosion resistance of the stainless steel increases significantly, manifesting as an increase in self-corrosion potential and a decrease in self-corrosion current density. Whereas examples 3 and 35% of the Cr content in example 3 and example 5 have a smaller difference in corrosion resistance, indicating that the stainless steel has a preferable Cr content of 29%, the effect of improving corrosion resistance is not obvious when the Cr content of the stainless steel is continuously increased, and the effect of improving the corrosion resistance gain by the addition of Cu, mo, W, nb and Ti is not obvious, and at the same time, excessive addition of Mo, W, nb and Ti significantly deteriorates the plastic formability of the stainless steel, so that the addition of the alloying element of example 3 is reasonable. Example 3 has good corrosion resistance under simulated fuel cell cathode and anode operating environments, and it has self-corrosion potential E corr And self-etching current density I corr Respectively-0.398 and-0.408V, 1.04×10 -7 And 8.96×10 - 8 A/cm 2 . Cr element is a key element affecting the passivation behavior of stainless steel, the matrix content of the Cr element directly affects the passivation behavior, the passivation capability of the Cr element in the highly corrosive environment is weak, the oxide content of Cr element with better corrosion resistance in the passivation film is reduced due to the lower Cr content in the embodiment 1 and the embodiment 2, the stability of the passivation film is poor, the self-corrosion potential is reduced and the self-corrosion current density is increased, and the Cr of the Cr element and the Cr element is reduced E /Ni E 4.8 and 5.1 respectively, which are lower than 5.5 of example 3, result in higher austenite phase content after the rolling annealing treatment, and micro-galvanic corrosion occurs due to different corrosion potentials of the austenite phase and the ferrite phase during corrosion, thereby remarkably reducing self-corrosion potential and increasing self-corrosion current densityLess additive and thus significantly reduces corrosion resistance.
The content of Ni, mo, W, cu in example 6 is the lowest, and since Ni element increases the corrosion potential of stainless steel, and Mo and W element increase the stability of passivation film, and thus decrease the corrosion current density, it has the lowest corrosion potential and the highest corrosion current density; example 7 reduced Ni content from 4% to 2% relative to example 3, the self-corrosion potential of the stainless steel was reduced from-0.398 and-0.408V to-0.437/-0.441V, respectively, with a slight reduction in corrosion current density in simulated fuel cell cathode (air-in) and anode (hydrogen-in) operating environments; example 8 WO formed upon corrosive dissolution due to the significant reduction in W element content compared to example 3 4 2- The ion concentration is lower, and the effect of improving the corrosion resistance is not obvious, so that the self-corrosion potential is lower and the self-corrosion current density is higher; the amounts of Nb and Ti elements in examples 9 and 10 are higher than the optimum range of the present invention, but the corrosion resistance substantially coincides with example 3 in the optimum range, however, the excessive amounts of Nb and Ti elements cause deterioration of the plastic formability, so that the addition amounts of Nb and Ti elements need to be strictly controlled within the above-mentioned ranges for the steel of the present invention.
At the fuel cell cathode operating voltage (0.23V VS. MSE) all example steels were in a passivated state and example 3 corrosion current density was 1.573×10 -5 A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the At the fuel cell anode operating voltage (-0.47V) VS. MSE) all example steels were in cathodic protection and example 3 corrosion current density was 2.752 ×10 -7 A/cm 2 The lower corrosion current density at the operating potential indicates that the passivation film has relatively good corrosion resistance.
Table 1 data for simulating potentiodynamic polarization testing of cathode/anode operating environment of fuel cell
The long-time constant potential polarization test can be carried out under the cathode and anode operation environment of the fuel cellAs can be seen from FIG. 3, example 3 has a corrosion current density of < 1×10 after 2270s of potentiostatic polarization at the cathode (air-through) operating voltage of the fuel cell -6 A/cm 2 Cathodic corrosion current density < 0.250X10 at polarization 14400s -6 A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the While the corrosion current density is always < -1×10 when the anode of the fuel cell is polarized at constant potential under the working voltage of hydrogen supply -6 A/cm 2 Corrosion current density < -0.336×10 at polarization 14400s -6 A/cm 2 This negative value of current indicates that example 3 is in a cathodic protection state under simulated anodic operating conditions with very little metal ion release from corrosion. The cathode and anode corrosion current densities of the example steels meet the U.S. department of energy DOE2025 standard < 1×10 -6 A/cm 2 The lower corrosion current density indicates better corrosion resistance in the cathode and anode environment working environments, less dissolution of stainless steel, less dissolution of released metal ions, and reduced toxic effects of metal ions on fuel cell membrane electrodes and proton exchange membranes.
The high corrosion resistance stainless steel of the bipolar plate of the fuel cell can be widely used in the fields of energy, electric power, chemical industry and daily life, and particularly relates to the field of manufacturing of bipolar plates for proton exchange membrane fuel cells.
Therefore, in summary, the high corrosion resistance low cost stainless steel of the invention completely meets the corrosion resistance requirements of the fuel cell cathode and anode in the working environment.
Claims (4)
1. The high corrosion resistance stainless steel for the fuel cell bipolar plate is characterized by comprising the following elements in percentage by mass: c is less than or equal to 0.01, cr is less than or equal to 25-35, ni is less than or equal to 0.5-4, si is less than or equal to 1, mn is less than or equal to 5.0, cu is less than or equal to 0.2-2.0, mo is less than or equal to 2-5.0, W is less than or equal to 0.1-1.5, N is less than or equal to 0.01, P is less than or equal to 0.02, S is less than or equal to 0.01, O is less than or equal to 0.001, and the mass percentages of Nb elements are: nb is more than or equal to 7.75×C+0.2, ti element is more than or equal to 3.43×N and less than or equal to 3.43×N+0.03, and the balance is Fe; wherein Cr is E /Ni E More than or equal to 5.5, the Cr E Is the following elementsSum of prime mass percentage relation, cr E =cr+mo+1.5si+0.5nb, the Ni E Ni is the sum of the following mass percent relation of each element E =Ni+30(C+N)+0.5Mn+0.25Cu。
2. The high corrosion resistant stainless steel for a fuel cell bipolar plate according to claim 1, wherein the high corrosion resistant stainless steel for a fuel cell bipolar plate comprises the following Cr elements in percentage by mass: cr=27 to 29.
3. The fuel cell bipolar plate high corrosion resistant stainless steel according to claim 1 or 2, wherein the mass percentage of Ni element in the fuel cell bipolar plate high corrosion resistant stainless steel is: ni=2 to 4.
4. The fuel cell bipolar plate high corrosion resistant stainless steel according to claim 3, wherein the mass percentage of the element W of the fuel cell bipolar plate high corrosion resistant stainless steel is: w=0.2-0.6, the mass percentage of the Mo element of the stainless steel with high corrosion resistance of the fuel cell bipolar plate is as follows: mo=2 to 4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410262926.1A CN117867412B (en) | 2024-03-08 | 2024-03-08 | High corrosion resistance stainless steel for fuel cell bipolar plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410262926.1A CN117867412B (en) | 2024-03-08 | 2024-03-08 | High corrosion resistance stainless steel for fuel cell bipolar plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117867412A true CN117867412A (en) | 2024-04-12 |
| CN117867412B CN117867412B (en) | 2024-05-10 |
Family
ID=90583371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410262926.1A Active CN117867412B (en) | 2024-03-08 | 2024-03-08 | High corrosion resistance stainless steel for fuel cell bipolar plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117867412B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102747301A (en) * | 2012-06-29 | 2012-10-24 | 宝山钢铁股份有限公司 | High-strength stainless steel cold-rolled sheet strip and manufacturing method thereof |
| CN110168122A (en) * | 2016-12-07 | 2019-08-23 | 霍加纳斯股份有限公司 | For producing the powder of stainless steel of two-phase sintering stainless steel |
| CN113355601A (en) * | 2021-05-31 | 2021-09-07 | 江苏省沙钢钢铁研究院有限公司 | Low-cost high-corrosion-resistant steel bar and production method thereof |
| US20230304118A1 (en) * | 2022-03-28 | 2023-09-28 | Jiangsu Wujin Stainless Steel Pipe Group Co., Ltd. | Method for Preparing Stainless Steel Seamless Tube with Ultra-High Cleanliness for Integrated Circuit and IC Industry Preparation Device, and Stainless Steel Seamless Tube |
| CN117431457A (en) * | 2023-10-16 | 2024-01-23 | 宁波宝新不锈钢有限公司 | Uncoated stainless steel bipolar plate for fuel cell and manufacturing method thereof |
| CN117551936A (en) * | 2023-11-15 | 2024-02-13 | 东北大学 | Fuel cell bipolar plate tungsten-nitrogen-containing high corrosion resistance stainless steel and preparation method thereof |
-
2024
- 2024-03-08 CN CN202410262926.1A patent/CN117867412B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102747301A (en) * | 2012-06-29 | 2012-10-24 | 宝山钢铁股份有限公司 | High-strength stainless steel cold-rolled sheet strip and manufacturing method thereof |
| CN110168122A (en) * | 2016-12-07 | 2019-08-23 | 霍加纳斯股份有限公司 | For producing the powder of stainless steel of two-phase sintering stainless steel |
| CN113355601A (en) * | 2021-05-31 | 2021-09-07 | 江苏省沙钢钢铁研究院有限公司 | Low-cost high-corrosion-resistant steel bar and production method thereof |
| US20230304118A1 (en) * | 2022-03-28 | 2023-09-28 | Jiangsu Wujin Stainless Steel Pipe Group Co., Ltd. | Method for Preparing Stainless Steel Seamless Tube with Ultra-High Cleanliness for Integrated Circuit and IC Industry Preparation Device, and Stainless Steel Seamless Tube |
| CN117431457A (en) * | 2023-10-16 | 2024-01-23 | 宁波宝新不锈钢有限公司 | Uncoated stainless steel bipolar plate for fuel cell and manufacturing method thereof |
| CN117551936A (en) * | 2023-11-15 | 2024-02-13 | 东北大学 | Fuel cell bipolar plate tungsten-nitrogen-containing high corrosion resistance stainless steel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117867412B (en) | 2024-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3202940A1 (en) | Ferritic stainless steel material, separator for solid polymer fuel cells which uses same, and solid polymer fuel cell | |
| CN117551936A (en) | Fuel cell bipolar plate tungsten-nitrogen-containing high corrosion resistance stainless steel and preparation method thereof | |
| CN109338247A (en) | A kind of cobalt improved austenitic stainless steel of copper zirconium and its process and heat treatment method | |
| WO2024051206A1 (en) | Hydrogen fuel cell bipolar plate base material and preparation method for foil thereof | |
| CN117867412B (en) | High corrosion resistance stainless steel for fuel cell bipolar plate | |
| CN109609866A (en) | A kind of cupric niobium cobalt high corrosion-resisting austenite stainless steel and its process and heat treatment method | |
| CN109355598A (en) | A kind of high corrosion resisting stainless steel of cupric zirconium cobalt and its process and heat treatment method | |
| CN109355465A (en) | A kind of cupric titanium cobalt high corrosion-resisting austenite stainless steel and its process and heat treatment method | |
| CN109355594B (en) | Copper-vanadium-cobalt modified stainless steel and processing and heat treatment method thereof | |
| CN108179360A (en) | A kind of super-purity ferrite stainless steel of tin copper synergistic effect and preparation method thereof | |
| CN110607490B (en) | Hafnium zirconium titanium reinforced austenitic stainless steel and preparation method thereof | |
| CN109355466A (en) | A kind of cupric tantalum cobalt high corrosion-resisting austenite stainless steel and its process and heat treatment method | |
| CN109504912A (en) | A kind of high corrosion resisting stainless steel of cupric titanium cobalt and its process and heat treatment method | |
| CN109355468A (en) | A kind of cobalt improved austenitic stainless steel of copper vanadium and its process and heat treatment method | |
| CN109609878A (en) | A kind of cobalt improved austenitic stainless steel of copper titanium and its process and heat treatment method | |
| CN109609869A (en) | A kind of cupric tungsten-cobalt high corrosion-resisting austenite stainless steel and its process and heat treatment method | |
| CN109355472B (en) | Copper-niobium-cobalt modified austenitic stainless steel and processing and heat treatment method thereof | |
| CN109355596B (en) | Copper-hafnium-cobalt-containing high-corrosion-resistance austenitic stainless steel and processing and heat treatment method thereof | |
| CN116254473B (en) | Battery bipolar plate, stainless steel and preparation method | |
| CN109609875A (en) | A kind of cobalt improved austenitic stainless steel of copper tantalum and its process and heat treatment method | |
| CN109504827A (en) | A kind of high corrosion resisting stainless steel of cupric tantalum cobalt and its process and heat treatment method | |
| CN109355471A (en) | A kind of modified austenitic stainless steel of copper tungsten-cobalt and its process and heat treatment method | |
| CN109504909A (en) | A kind of high corrosion resisting stainless steel of cupric hafnium cobalt and its process and heat treatment method | |
| CN109609865A (en) | A kind of cobalt improved austenitic stainless steel of copper hafnium and its process and heat treatment method | |
| CN109355467A (en) | A kind of copper hafnium cobalt austenitic stainless steel against corrosion and its process and heat treatment method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |