CN116657013A - Metal ceramic material V, zr, cr doped modified titanium silicon carbon for bipolar plate of proton exchange membrane fuel cell and preparation method thereof - Google Patents
Metal ceramic material V, zr, cr doped modified titanium silicon carbon for bipolar plate of proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- DXZIFGZIQQRESB-UHFFFAOYSA-N [C].[Ti].[Si] Chemical class [C].[Ti].[Si] DXZIFGZIQQRESB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000446 fuel Substances 0.000 title claims abstract description 40
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 230000007797 corrosion Effects 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004088 simulation Methods 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 239000011195 cermet Substances 0.000 claims 4
- 150000003608 titanium Chemical class 0.000 claims 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 11
- 239000010439 graphite Substances 0.000 abstract description 11
- 239000006104 solid solution Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000013590 bulk material Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- -1 SO 4 2- Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- 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
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Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell and a preparation method thereof, wherein the metal ceramic material is a V, zr and Cr doped modified titanium silicon carbon material, and the chemical formula of the modified titanium silicon carbon material is (Ti 1‑x N x ) 3 SiC 2 . The modified titanium-silicon-carbon material prepared by the invention has the excellent performances of metal and ceramic, has good electric conductivity and heat conductivity at normal temperature as the same as the metal, has higher elastic modulus, has certain ductility at normal temperature, and can be machined like the metal and graphite; meanwhile, the ceramic material has the characteristics of ceramic material, and has high yield strength, high melting point, high thermal stability and excellent corrosion resistance; in addition, elements such as V, zr, cr and the like are solid-solution doped at the Ti position, so that the corrosion resistance of the titanium silicon carbon block can be greatly improved, and the titanium silicon carbon block can stably work in the working environment of the PFMFC.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the characteristics of zero emission and zero pollution, are clean and environment-friendly power generation technologies, and are ultimate energy power solutions. As one of the key components of the fuel cell, the bipolar plate has the function of separating fuel, oxidant and coolant, uniformly supplying the fuel and the oxidant to the electrode through the flow channel for electrochemical reaction, distributing the coolant to each cooling cavity, removing heat generated by the reaction, and collecting current electrochemically generated on the single cell. Meanwhile, the bipolar plate plays a role in supporting the single fuel cell, and the single fuel cell is sequentially connected to form a galvanic pile. Therefore, the bipolar plate needs to meet the requirements of high conductivity and thermal conductivity, high mechanical strength, effective reaction fluid blocking, good corrosion resistance, low material cost, large-scale automatic production and the like.
Currently, bipolar plates are mainly composed of three types, namely graphite bipolar plates, metal bipolar plates and composite bipolar plates. Graphite has the most traditional bipolar plate material with high strength, high density and excellent electric and heat conductivity, and the excellent durability and corrosion resistance can meet the acidic working environment of the PEMFC battery stack, so the graphite is the bipolar plate material with the most application at present. However, graphite itself is a porous structure, and the pores are blocked by a specific process during processing, and even so it is difficult to ensure the final gas barrier properties of the graphite bipolar plate; moreover, graphite is brittle and fragile, and cannot be madeThe thin plate has long cutting processing period and high graphitization temperature, so the processing difficulty is high, the cost is high, the volume is large, and the volume power density of the galvanic pile is difficult to further improve, thereby limiting the commercial development and application of the thin plate on a passenger car. The metal bipolar plate has high strength, is easy to process, is easy to realize large-scale production, and can improve the specific power of the fuel cell. But the bipolar plate working environment has a plurality of corrosive ions, such as SO 4 2- 、F - And the like, the metal bipolar plate material is easy to corrode, a passivation layer is formed, the contact resistance between the bipolar plate and the diffusion layer is increased, and the output power and the durability of the fuel cell stack are greatly affected. The metal/carbon composite bipolar plate is formed by combining metal and graphite, a metal sheet is used as a substrate, a graphite material is used as a flow field, the metal is prevented from directly contacting an electrode to be corroded, the corrosion resistance of the graphite bipolar plate is maintained, the metal bipolar plate has excellent conductivity and gas impermeability, the volume and the mass of the whole cell stack are reduced, and the volume ratio power and the mass ratio power are high. Although the composite bipolar plate has excellent performance, a great deal of research is needed to ensure the conductivity, mechanical property and long-term stability of the composite bipolar plate, and the processing cost of the composite bipolar plate is far less than the requirement of mass production. Therefore, the development of a novel PEMFC bipolar plate material has very important practical significance.
Disclosure of Invention
The invention aims to solve the problems of graphite bipolar plates, metal bipolar plates and composite bipolar plates adopted by PEMFCs in the prior art, and provides a metal ceramic material for proton exchange membrane fuel cell bipolar plates and a preparation method thereof. The modified titanium silicon carbon metal ceramic material has a practical prospect on PEMFC, and can make great contribution to the development of bipolar plate materials.
The technical scheme of the invention is as follows:
a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell is a V, zr and Cr doped modified titanium silicon carbon material, wherein the chemical formula of the modified titanium silicon carbon material is (Ti 1-x N x ) 3 SiC 2 Wherein N is any one or more of V, zr and Cr, and x is 0.01-0.15.
Further, the density of the modified titanium silicon carbon is (4.45-4.65) g/cm 3 The density is lower than that of stainless steel materials, and the quality of a galvanic pile can be reduced.
Further, the density of the modified titanium silicon carbon is higher than 90%, preferably higher than 95%, so that the problem of gas leakage in the service process can be avoided.
A preparation method of a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell comprises the following steps:
raw materials of Ti powder, N powder, silicon powder and graphite powder are prepared from the following components in percentage by atom: n: si: c=3 (1-x): 3x:1:2, mixing the prepared raw material powder with alcohol, ball-milling for 5-48 h, and airing for later use; then cold pressing is carried out under the pressure condition of 5-15 MPa, argon is adopted as shielding gas, sintering is carried out in a hot pressing sintering furnace with the temperature of 1450-1750 ℃, and the temperature is kept for 30-75 min.
Further, x is 0.01 to 0.15; the N powder is any one or more of V metal powder, zr metal powder and Cr metal powder.
Further, the pressure in the hot pressing sintering furnace is 40-60 MPa.
The single-phase materials are synthesized by the preparation process, and the single-phase materials V, zr and Cr are doped and modified to be used as the bipolar plate of the proton exchange fuel cell, which belongs to the first example in the field. The modified titanium-silicon-carbon material has the excellent performances of metal and ceramic, has good electric conductivity and heat conductivity at normal temperature as well as high elastic modulus as metal, has ductility at normal temperature, and can be machined like metal and graphite; meanwhile, the ceramic material has the characteristics of ceramic material, and has high yield strength, high melting point, high thermal stability and excellent corrosion resistance. In addition, elements such as V, zr, cr and the like are doped in solid solution at the Ti position, so that the corrosion resistance of the titanium silicon carbon block can be greatly improved, and the titanium silicon carbon block can stably work in the working environment of the PFMFC.
The application of the metal ceramic material for the bipolar plate of the proton exchange membrane fuel cell in preparing the bipolar plate of the proton exchange membrane fuel cell.
Further, the conductivity of the modified titanium silicon carbon material at room temperature is (4.0-4.8) multiplied by 10 6 Ω -1 ·m -1 Can ensure that the bipolar plate has good conductivity.
Further, the thermal conductivity of the modified titanium silicon carbon material at room temperature is (32-39) W/m.K, so that the bipolar plate can be ensured to have high heat conduction capability.
Further, in the fuel cell simulation environment (H 2 SO 4 The electrokinetic potential test is carried out in the condition that the concentration is 0.5mol/L+2ppm HF and the temperature is 80 ℃, and the corrosion current density of the ceramic bipolar plate of the proton exchange membrane fuel cell is 0.04-0.95 mu A/cm 2 [ self-etching potential of 0.12-0.37V (vs. SCE)]。
Further, at an assembly force of 150N/cm 2 Under the condition that the contact resistance of the modified titanium silicon carbon material is 0.3-9.0 mΩ cm 2 。
The invention has the beneficial effects that:
the V, zr and Cr doped modified titanium silicon carbon metal ceramic material prepared by the invention has excellent performance, and comprises the following components:
(1) Higher conductivity; can ensure that the bipolar plate has good conductivity;
(2) Higher heat conducting property; the high thermal conductivity of the metal ceramic material can ensure that the bipolar plate has high heat conduction capacity;
(3) The thermal stability is good; the metal ceramic material is a single-phase material, the thermal decomposition temperature is more than 1580 ℃, the bond strength is high, the structure is stable, the material can not be denatured in the service period, and structural failure is avoided;
(4) The creep resistance is high; the high creep resistance can reduce creep failure and reduce mechanical damage in the service process of the bipolar plate;
(5) The processing is easy; the processing performance is good, and the processing cost of the bipolar plate material can be reduced;
(6) Corrosion resistance; the metal ceramic material has good corrosion resistance and can prevent the corrosion of the surface in the service process; meanwhile, elements such as V, zr, cr and the like are solid-solution doped at the Ti position, so that the corrosion resistance of the titanium silicon carbon block can be greatly improved, and the damage to the electrode and the increase of the surface resistance are avoided;
(7) Has high elastic modulus; the internal consumption of the modified titanium silicon carbon material is not increased basically below 1020 ℃.
Drawings
FIG. 1 shows a V-doped modified titanium-silicon-carbon material (Ti) prepared in example 1 0.95 V 0.05 ) 3 SiC 2 A surface topography of the block;
FIG. 2 shows the simulation of a V-doped titanium-silicon-carbon material in a fuel cell environment (H 2 SO 4 0.5mol/L+2ppm HF, at 80 ℃ C.) and electrokinetic potential testing;
FIG. 3 is a schematic diagram of a Cr-doped modified titanium-silicon-carbon material (Ti 0.98 Cr 0.02 ) 3 SiC 2 SEM image of the block.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
For a further understanding of the present invention, reference will now be made to the drawings and examples.
Example 1
A preparation method of a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell adopts a V-doped titanium silicon carbon material in the embodiment, and comprises the following steps:
ti, V, si and C element powder are adopted as original synthetic materials, and according to Ti: v: si: c=2.85: 0.15:1:2, preparing raw material powder in proportion, mixing the prepared raw material powder with alcohol, putting the mixture into a ball ink tank for ball milling for 10 hours, taking out, sieving and airing for standby; the cold pressing is carried out under the pressure of 7MPa, then sintering is carried out under the pressure of 40MPa at maximum in a hot pressing sintering furnace under the argon environment, and the temperature is kept at 1600 ℃ for 75min.
The prepared metal ceramic material is V-doped modified titanium silicon carbon material, and the chemical formula of the metal ceramic material is (Ti 0.95 V 0.05 ) 3 SiC 2 As shown in FIG. 1, the densification (Ti 0.95 V 0.05 ) 3 SiC 2 Surface topography of the block.
The bulk material has a density of 98.5% as determined by the archimedes method (ISO 18754). Cutting phi 30X 5mm, 4X 40mm from sintered compact bulk material by wire cutting 3 And 10X 2mm 3 Is then polished with 400# sic sandpaper, 600# sic sandpaper, 800# sic sandpaper, 1000# sic sandpaper, then polished with a polishing paste having a particle size w=1, and finally ultrasonically cleaned with alcohol for further experimentation.
The density of the sample was 4.48g/cm 3 Four-point method test (Ti 0.95 V 0.05 ) 3 SiC 2 The room temperature resistivity of the block was 4.49×10 6 Ω -1 ·m -1 By unsteady state method (Ti 0.95 V 0.05 ) 3 SiC 2 The thermal conductivity of the block was 36W/mK. In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing is carried out in 0.5mol/L and 2ppmHF solution at 80 ℃ and assembling force is 50-200N/cm 2 Under the condition of testing Ti 3 SiC 2 Contact resistance of bulk material.
The V-doped modified titanium-silicon-carbon material is shown in FIG. 2 in a simulated fuel cell environment (H 2 SO 4 Electrokinetic potential testing was performed at a concentration of 0.5mol/L+2ppm HF at a temperature of 80 ℃) to obtain a polarization profile.
Test results showed that in a fuel cell simulation environment (H 2 SO 4 The corrosion current density of the V-doped modified titanium silicon carbon material in the HF solution with the concentration of 0.5mol/L and the temperature of 2ppm is 80 ℃ is 0.42 mu A/cm 2 [ Corrosion potential 0.18V (vs. SCE)]The ASR was 1.9mΩ·cm at a pressure of 1.4MPa -2 Meets DOE performance index, and shows that the V-doped modified titanium-silicon-carbon material can be used for proton exchange membrane fuel cell bipolar plate material.
Example 2
A preparation method of a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell adopts Zr doped titanium silicon carbon material in the embodiment, and comprises the following steps:
ti, zr, si and C element powder are adopted as original synthetic materials, and the following Ti: zr: si: c=2.7: 0.3:1:2, preparing raw material powder in proportion, mixing the prepared raw material powder with alcohol, putting the mixture into a ball ink tank for ball milling for 30 hours, taking out, sieving and airing for later use; the cold pressing is carried out under the pressure of 10MPa, then sintering is carried out under the pressure of 60MPa at maximum in a hot pressing sintering furnace under the argon environment, and the temperature is maintained at 1620 ℃ for 60min.
The prepared metal ceramic material is Zr doped modified titanium silicon carbon material, and the chemical formula is (Ti 0.9 Zr 0.1 ) 3 SiC 2 。
The bulk material has a density of 99.3% as determined by the archimedes method (ISO 18754). Cutting phi 30X 5mm, 4X 40mm from sintered compact bulk material by wire cutting 3 And 10X 2mm 3 Is then polished with 400# sic sandpaper, 600# sic sandpaper, 800# sic sandpaper, 1000# sic sandpaper, then polished with a polishing paste having a particle size w=1, and finally ultrasonically cleaned with alcohol for further experimentation.
The density of the sample was 4.51g/cm 3 Four-point method test (Ti 0.9 Zr 0.1 ) 3 SiC 2 The room temperature resistivity of the block was 4.67×10 6 Ω -1 ·m -1 By unsteady state method (Ti 0.9 Zr 0.1 ) 3 SiC 2 The thermal conductivity of the block was 38W/mK.
In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was performed in HF solution at a concentration of 0.5mol/L and 2ppm at 80℃with a corrosion current density of 0.53. Mu.A/cm 2 [ Corrosion potential 0.252V (vs. SCE)]. At an assembly force of 50-200N/cm 2 Under the condition, the contact resistance of the Zr-doped titanium-silicon-carbon block material is tested to be 150N/cm 2 Under the condition that the contact resistance is 6mΩ·cm 2 。
Example 3
A preparation method of a metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell adopts Cr-doped titanium silicon carbon material in the embodiment, and comprises the following steps:
ti, cr, si and C element powder are adopted as raw synthetic materials, and the following Ti: cr: si: c=2.94: 0.06:1:2, preparing raw material powder in proportion, mixing the prepared raw material powder with alcohol, putting the mixture into a ball ink tank for ball milling for 30 hours, taking out, sieving and airing for later use; the cold pressing is carried out under the pressure of 5MPa, then sintering is carried out under the pressure of 50MPa at maximum in a hot pressing sintering furnace under the argon environment, and the temperature is kept at 1600 ℃ for 70min.
The prepared metal ceramic material is a Cr-doped modified titanium silicon carbon material, and the chemical formula of the metal ceramic material is (Ti 0.98 Cr 0.02 ) 3 SiC 2 As shown in FIG. 3, the (Ti 0.98 Cr 0.02 ) 3 SiC 2 SEM image of the block.
The bulk material has a density of 98.3% as determined by the archimedes method (ISO 18754). Cutting phi 30X 5mm, 4X 40mm from sintered compact bulk material by wire cutting 3 And 10X 2mm 3 Is then polished with 400# sic sandpaper, 600# sic sandpaper, 800# sic sandpaper, 1000# sic sandpaper, then polished with a polishing paste having a particle size w=1, and finally ultrasonically cleaned with alcohol for further experimentation.
The density of the sample was 4.53g/cm 3 Four-point method test (Ti 0.98 Cr 0.02 ) 3 SiC 2 Room temperature resistivity of the block was 4.12X10 6 Ω -1 ·m -1 By unsteady state method (Ti 0.98 Cr 0.02 ) 3 SiC 2 The thermal conductivity of the block was 32W/mK.
In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was performed in HF solution at a concentration of 0.5mol/L and 2ppm at 80deg.C, with an etching current density of 0.04 μA/cm 2 [ Corrosion potential 0.314V (vs. SCE)]. At an assembling force of 50-200N/cm 2 Under the condition, the contact resistance of the Cr-doped titanium-silicon-carbon block material is tested to be 150N/cm 2 Under the condition that the contact resistance is 3mΩ·cm 2 。
The foregoing description is only a preferred embodiment of the present invention and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or that equivalents may be substituted for part of the technical features thereof. Any modification, equivalent replacement, variation, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A metal ceramic material for a bipolar plate of a proton exchange membrane fuel cell is characterized in that the metal ceramic material is a V, zr and Cr doped modified titanium silicon carbon material, and the chemical formula of the modified titanium silicon carbon material is (Ti 1-x N x ) 3 SiC 2 Wherein N is any one or more of V, zr and Cr, and x is 0.01-0.15.
2. The cermet material for a bipolar plate of a proton exchange membrane fuel cell according to claim 1 wherein the density of the modified titanium silicalite is (4.45-4.65) g/cm 3 。
3. Cermet material for a bipolar plate of a proton exchange membrane fuel cell according to claim 1, characterized in that the density of the modified titanium silicalite is higher than 90%, preferably higher than 95%.
4. A method of preparing a cermet material for a bipolar plate of a proton exchange membrane fuel cell according to any of claims 1-3 comprising the steps of:
raw materials of Ti powder, N powder, silicon powder and graphite powder are prepared from the following components in percentage by atom: n: si: c=3 (1-x): 3x:1:2, mixing the prepared raw material powder with alcohol, ball-milling for 5-48 h, and airing for later use; then cold pressing is carried out under the pressure condition of 5-15 MPa, argon is adopted as shielding gas, sintering is carried out in a hot pressing sintering furnace with the temperature of 1450-1750 ℃, and the temperature is kept for 30-75 min.
5. The method according to claim 4, wherein x is 0.01 to 0.15; the N powder is any one or more of V metal powder, zr metal powder and Cr metal powder.
6. Use of a cermet material for a bipolar plate of a proton exchange membrane fuel cell according to any of claims 1-3 for the preparation of a bipolar plate of a proton exchange membrane fuel cell.
7. The use according to claim 6, wherein the modified titanium silicon carbon material has a conductivity of (4.0-4.8) x 10 at room temperature 6 Ω -1 ·m -1 。
8. The use according to claim 6, wherein the modified titanium silicon carbon material has a thermal conductivity of (32-39) W/m-K at room temperature.
9. Use according to claim 6, characterized in that in the fuel cell simulation environment (H 2 SO 4 The electrokinetic potential test is carried out in the condition that the concentration is 0.5mol/L+2ppm HF and the temperature is 80 ℃, and the corrosion current density of the ceramic bipolar plate of the proton exchange membrane fuel cell is 0.04-0.95 mu A/cm 2 [ self-etching potential of 0.12-0.37V (vs. SCE)]。
10. The use according to claim 6, characterized in that, inThe assembly force is 150N/cm 2 Under the condition that the contact resistance of the modified titanium silicon carbon material is 0.3-9.0 mΩ cm 2 。
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| CN202310451924.2A CN116657013A (en) | 2023-04-25 | 2023-04-25 | Metal ceramic material V, zr, cr doped modified titanium silicon carbon for bipolar plate of proton exchange membrane fuel cell and preparation method thereof |
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| CN202310451924.2A CN116657013A (en) | 2023-04-25 | 2023-04-25 | Metal ceramic material V, zr, cr doped modified titanium silicon carbon for bipolar plate of proton exchange membrane fuel cell and preparation method thereof |
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