CN115852411A - Bipolar plate for hydrogen production by PEM water electrolysis and preparation method thereof - Google Patents
Bipolar plate for hydrogen production by PEM water electrolysis and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bipolar plate for hydrogen production by PEM water electrolysis and a preparation method thereof, belonging to the field of hydrogen production by water electrolysis. The flow field structure is a combination of a trapezoid structure and a rectangular structure, wherein one half of the flow field structure close to the inlet of the cathode or the anode is in a rectangular shape, one half of the flow field structure close to the outlet of the cathode or the anode is in a trapezoid shape, the joint of the flow fields of the two structures is an array point-shaped multifunctional area, and the composite flow field structure is a two-layer structure of a macroporous titanium layer and a microporous titanium layer; the invention also discloses a preparation method of the multi-shape integrated water electrolysis metal bipolar plate composite flow field, which is characterized in that different titanium sizing agents are printed on the alloy steel plate in a mould printing mode to prepare a composite structure forming the water electrolysis bipolar plate flow field.
Description
Technical Field
The invention belongs to the field of hydrogen production by water electrolysis, and particularly relates to a bipolar plate for hydrogen production by PEM water electrolysis and a preparation method thereof.
Background
Hydrogen is becoming increasingly popular as a clean energy source. The PEM water electrolysis technology can obtain hydrogen by utilizing the redundant energy generated by wind energy and light energy. Proton exchange membrane water electrolysis has many advantages. The only raw material in this process is water and the products are oxygen and hydrogen. The obtained gas has high purity, safety, high efficiency and environmental protection, can realize on-site hydrogen production, and solves the problem of hydrogen transportation. Therefore, the proton exchange membrane water electrolysis technology has important application in the fields of energy, traffic, chemical industry and the like.
In the water electrolysis reaction process, the anode loses electrons to generate oxygen, the cathode obtains electrons to generate hydrogen, and the bipolar plate is one of the key technologies of the proton exchange membrane water electrolysis technology. It has the functions of supporting, gas isolating, conducting and heat dissipating in the water and electric digestion pool. Therefore, there are high demands on the mechanical properties, electrical conductivity, thermal conductivity, chemical stability and cost of the bipolar plate material. When the traditional water electrolysis bipolar plate comprises a hydrogen frame, an oxygen frame and a partition plate, multiple complex processes such as positioning, gluing, hot pressing, welding and the like are required to be carried out, for example, CN104716329B firstly independently processes each component of the bipolar plate; conducting treatment on the partition plate; finally, the bipolar plate is welded into a complete bipolar plate after being fixed and formed. Due to the particularity of the water electrolysis operation environment, the material of the water electrolysis bipolar plate is generally pure titanium or other high corrosion-resistant and conductive materials, so that the preparation cost is greatly increased, and the price of the high alloy steel plate is low. However, when the water electrolysis is performed, the flow field is in a water-gas coexisting state, and no matter for the anode or the cathode, at the inlet of the anode or the inlet of the cathode of the water electrolysis, the hydrogen and the oxygen generated by the water electrolysis are discharged out of the electrolytic cell along with the flow of the liquid at the beginning of the reaction, so that how to realize the rapid discharge of the gas and not influence the occurrence of the subsequent reaction is the key for improving the water electrolysis performance.
Disclosure of Invention
The invention aims to provide a bipolar plate for hydrogen production by PEM water electrolysis and a preparation method thereof.
The technical purpose of the invention is realized by the following technical scheme:
a bipolar plate for hydrogen production by PEM water electrolysis takes an alloy steel plate as a substrate, and the surface of the substrate is sequentially provided with a microporous titanium layer a, a macroporous titanium layer and a microporous titanium layer b;
the pore diameters of the microporous titanium layer a and the microporous titanium layer b are both 100nm-10 microns, and the pore diameter of the macroporous titanium layer is larger than 10 microns and less than or equal to 100 microns;
the microporous titanium layer a at least comprises spherical dehydrotitanium powder, the macroporous titanium layer at least comprises spherical atomized titanium powder with the particle size of 50-100 mu m and a pore-forming agent, and the microporous titanium layer b at least comprises spherical atomized titanium powder with the particle size of 20-50 mu m;
the composite flow field structure of the bipolar plate is formed by the macroporous titanium layer and the microporous titanium layer b, the composite flow field structure comprises a trapezoidal flow channel ridge, a functional area and a rectangular flow channel ridge, the rectangular flow channel ridge is located close to a cathode inlet or an anode inlet and is connected with one side of a material inlet and the functional area, the trapezoidal flow channel ridge is located close to a cathode outlet or an anode outlet and is connected with the other side of the material outlet and the functional area, and the functional area is columnar in an array. The invention is further configured to: the height of the trapezoidal flow channel ridge and the height of the rectangular flow channel ridge are both 0.3-1mm, the width of the groove bottom of the trapezoidal flow channel is 0.2-0.5mm, the width of the opening of the trapezoidal flow channel is 0.4-1mm, and the width of the groove of the rectangular flow channel is 0.5-1mm.
The invention is further configured to: the thickness of the microporous titanium layer a is 0.1-0.4mm; the thickness of the macroporous titanium layer and the thickness of the microporous titanium layer b are both 0.3-0.5mm.
The invention is further configured to: the particle size of the spherical dehydrogenation titanium powder is 30-100 mu m; the macroporous titanium layer comprises spherical atomized titanium powder with the particle size of 50-100 mu m, a solvent, a binder, a pore-forming agent and a plasticizer; the microporous titanium layer b comprises spherical atomized titanium powder with the particle size of 20-50 mu m, a solvent, a binder and a plasticizer.
The invention is further configured to: the solvent in the macroporous titanium layer and the microporous titanium layer b is independently at least one of ethanol, toluene or methanol, the binder in the macroporous titanium layer and the microporous titanium layer b is independently at least one of polyvinyl butyral resin or acrylic resin, the plasticizer in the macroporous titanium layer and the microporous titanium layer b is independently at least one of dioctyl phthalate, dibutyl phthalate or propylene glycol diacetate polyester, and the pore-forming agent comprises one or a combination of more than two of urea, ammonium bicarbonate, sodium carbonate and oxalic acid.
The invention is further configured to: in the macroporous titanium layer, the mass ratio of spherical atomized titanium powder, a solvent, a binder, a pore-forming agent and a plasticizer is 20-40:52-64:2-10:3-4:1-2; in the microporous titanium layer b, the mass ratio of spherical atomized titanium powder, solvent, binder and plasticizer is 60-80:15-35:3-4:1-2.
The invention is further configured to: the thickness of the alloy steel plate is 0.5-1mm, the alloy steel plate contains one or more of Ni, ti and Mo alloy elements, and the mass content of the total alloy elements is 10-30 wt.%.
The invention also provides a preparation method of the bipolar plate for hydrogen production by PEM water electrolysis, which comprises the following steps:
(1) Preparing the slurry of the macroporous titanium layer: stirring and mixing spherical atomized titanium powder with the particle size of 50-100 mu m with a solvent, a binder, a pore-forming agent and a plasticizer to obtain macroporous titanium layer slurry;
preparing a microporous titanium layer b slurry: stirring and mixing spherical atomized titanium powder with the particle size of 20-50 mu m, a solvent, a binder and a plasticizer to obtain slurry of a microporous titanium layer b;
(2) Pretreating an alloy steel plate;
(3) Spraying spherical dehydrotitanium powder to the surface of the alloy steel plate obtained by pretreatment in a plasma spraying mode to form a microporous titanium layer a;
(4) Printing the macroporous titanium layer slurry on the microporous titanium layer a by adopting a mould printing mode, and drying and demoulding;
(5) Transferring to a vacuum furnace, and carrying out temperature programming sintering to prepare a metal pole plate with a macroporous titanium layer;
(6) And printing the slurry of the microporous titanium layer b onto the macroporous titanium layer in a mould printing mode, drying and demolding to form the microporous titanium layer b on the surface of the macroporous titanium layer, and preparing the water electrolysis bipolar plate.
The invention is further configured to: the plasma spraying conditions are as follows: the enthalpy of the plasma is 22-50MJ/kg; the spraying speed is 600-1000mm/s; the spraying temperature is 150-200 ℃.
The invention is further configured to: the conditions of the temperature programming are as follows: argon protection flow: 10-100mL/min, vacuum: -0.1 to-0.9 MPa, time: 30-100min; rate of temperature rise: 5-20 ℃/min; the roasting temperature is 600-1300 ℃.
The invention is further configured to: the drying temperature is 100-150 deg.C, and the drying time is 3-5min.
The invention is further configured to: the pretreatment of the alloy steel plate comprises the following steps: and (3) polishing, polishing and cleaning the surface of the alloy steel plate, then putting the alloy steel plate into an acetone solution for ultrasonic cleaning, taking the alloy steel plate out, using ultrapure water for ultrasonic cleaning, taking the alloy steel plate out, and blow-drying the alloy steel plate for later use.
The invention is further configured to: the polishing is performed step by using sand paper with 500-1200 meshes.
The invention is further configured to: the polishing adopts sand paper with the mesh number of 500, 700, 900 and 1200 meshes to polish step by step.
The invention is further configured to: the steps (3) - (4) are completed by adopting a continuous production line with an annular guide rail, a plurality of electrically driven sliding blocks are arranged on the annular guide rail, and stainless steel plates are placed on the sliding blocks; be equipped with plasma spraying district, thickness detection district, mould printing district, no. two thickness detection districts on the line is produced to the continuous type in proper order, ring rail and the line is produced to the continuous type all with control system circuit connection.
The invention has the following beneficial effects:
1. the performance is high: the invention adopts the structure of the composite flow field, the shape of the flow field near the inlet of the cathode and the anode is rectangular, the shape of the flow field near the outlet of the cathode and the anode is trapezoidal, and because the electrochemical reaction starts at the inlet and generates hydrogen and oxygen, the gas in the flow field is less, and the rectangular flow channel can realize good gas transmission effect. The gas accumulated in the flow field is more and more near the outlet of the cathode and the anode, so the shape of the flow field near the outlet of the cathode and the anode is set to be trapezoidal, the opening area of the flow field is increased, the contact area of the bipolar plate flow field opening and the membrane electrode is increased, the reaction is ensured to be carried out, the timely discharge of the generated hydrogen and oxygen is improved, the mass transfer balance among the reaction water, the generated gas and the surplus water in the flow field is improved, and the integral water electrolysis performance is improved.
2. The interlayer bonding force is strong: according to the invention, before the flow field structure is printed, the high alloy steel plate is subjected to plasma spraying, namely, the micro-pore titanium layer is sprayed on the surface of the high alloy steel plate in a plasma spraying manner, so that titanium particles with small particle sizes can permeate into the surface of steel, the distribution is denser and more uniform, the contact resistance is effectively reduced, the binding force between the high alloy steel plate and the titanium layer is increased, and then the macro-pore titanium layer and the micro-pore titanium layer b are prepared in a printing manner, so that the mutual permeation of the titanium particles between the layers can be effectively enhanced by combining the influence of printing pressure, and the binding force between the titanium layer and the high alloy steel plate is further improved.
3. The transmission capacity is strong: the invention is provided with a composite layer structure of a flow field, firstly preparing a microporous titanium layer a on the surface of a high alloy steel plate by a plasma spraying means, then preparing the flow field structure on the microporous titanium layer a by utilizing mould printing, then carrying out vacuum sintering on the flow field structure to form a macroporous flow field structure, finally printing high-concentration microporous titanium layer b slurry on the macroporous flow field again, reducing the condition of permeating into macropores by the high-concentration microporous titanium slurry, finally forming a composite flow field structure, forming the macroporous structure at the bottom of a groove of the flow field, increasing the flow of liquid and gas, improving the mass transfer capacity of the macroporous flow field structure, increasing the conductivity of the microporous titanium layer structure and a membrane electrode and reducing the contact resistance of the microporous titanium layer structure on the ridge of the flow field, and in addition, the invention also adds a columnar multifunctional area of an array at the joint of the bipolar plates of the two flow field structures, diversifying the flow path of the liquid in the flow field, being beneficial to the conversion distribution and conduction of the liquid in the two flow fields with different shapes, combining the mutual superposition of the titanium layers with different apertures, and improving the output performance of the whole water electrolysis.
4. The preparation cost is low: compared with the traditional method for preparing the water electrolysis bipolar plate by using the pure titanium plate, the method for preparing the water electrolysis bipolar plate by using the pure titanium plate has the advantages that the titanium layer is prepared on the metal high alloy steel plate base material, the flow field and the multifunctional area are integrally formed, and the preparation cost is greatly reduced. The invention can integrally prepare the water electrolysis bipolar plate, the separation plate and the oxyhydrogen frame are respectively machined and formed in the traditional preparation process, and then are bonded by glue to realize the assembly and the formation of the bipolar plate, so that the bonding strength and the integrity can influence the resistance, the air tightness and the like of the bipolar plate due to the existence of the glue.
5. According to the invention, a continuous production line with an annular guide rail is adopted, and then the thickness detection equipment and the intelligent measurement and control of a control system are adopted, so that the circulating transmission of a batch of stainless steel plates on the production line can be realized to realize continuous preparation; according to the design of the annular guide rail, the stainless steel plate is fully cooled after plasma spraying and naturally dried after mould printing on the premise of not needing to enlarge the length of the conveying rail before the drying process of the oven, so that continuous preparation can be realized by subsequent spraying and printing processes for multiple times; in addition, the preparation can be completed by circularly conveying the stainless steel plates on the premise of not increasing the number of equipment, so that the cost is saved, and the problem that the product percent of pass is influenced by the problem that the debugging of a plurality of pieces of equipment is not unified is effectively avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic view of a mold.
Fig. 2 is a trapezoidal partial section of the mold.
Fig. 3 is a rectangular partial section of the mold.
Figure 4 is a cross-section of a bipolar plate trapezoidal flow field.
Figure 5 is a rectangular flow field cross section of a bipolar plate.
In the figure: 1. opening a trapezoidal flow field die; 2. opening a functional area flow field mold; 3. opening a rectangular flow field mold; 1-1, a trapezoidal flow field injection port; 3-1, a rectangular flow field injection port; 4. a trapezoidal flow channel groove; 4-1, opening of the trapezoidal flow channel; 4-2, trapezoidal flow channel ridge; 2-1, functional area; 5. a rectangular runner groove; 6. rectangular flow channel ridge.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Preparing the slurry of the macroporous titanium layer: 20g of spherical atomized titanium powder (obtained by atomization treatment and prepared by a method common in the art) with the particle size of 50 μm, 64g of absolute ethyl alcohol, 10g of polyvinyl butyral resin, 4g of ammonium bicarbonate and 2g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Preparing a microporous titanium layer b slurry: 60g of spherical atomized titanium powder with the particle size of 20 mu m, 35g of absolute ethyl alcohol, 4g of polyvinyl butyral resin and 1g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Cutting a piece of high alloy steel with the thickness of 0.5mm and the Mo alloy mass content of 30% and the area of 20cm x 10cm, grinding and polishing step by using 200-500-mesh abrasive paper, then putting the high alloy steel plate into an acetone solution, ultrasonically cleaning for 3 times, cleaning for 10min each time, then cleaning by using ultrapure water, and taking out and drying.
Putting the cleaned high-alloy steel plate on a plasma spraying platform, and setting the condition of a spraying machine to be 22MJ/kg of plasma enthalpy; the spraying speed is 600mm/s; the spraying temperature is 150 ℃, spherical dehydrotitanium powder (obtained by dehydrogenation treatment and prepared by a method commonly used in the field) with the grain diameter of 30 mu m is sprayed on the surface of the high alloy steel to form a micropore titanium layer a with the thickness of 0.1mm, and the pore diameter of the micropore titanium layer a is 10 mu m. And then placing the mold on the surface of the high alloy steel, printing the macroporous titanium layer slurry on the surface of the microporous titanium layer a according to the shape of the mold, wherein the thickness is 0.3mm, then placing the microporous titanium layer slurry into a 100 ℃ oven for heat treatment for 5min, taking out the microporous titanium layer slurry after the time is up, placing the microporous titanium layer slurry into a-0.1 MPa vacuum furnace, carrying out the heat treatment at 1300 ℃ for 30min, carrying out argon protection flow of 10mL/min, and taking out the microporous titanium layer slurry after the time is up to obtain the metal pole plate with the macroporous titanium layer with the aperture of 100 microns. And then placing a mould on the surface of the macroporous titanium layer, printing the slurry of the microporous titanium layer b to the surface of the macroporous titanium layer along the shape of the mould with the thickness of 0.3mm, drying again at the temperature of 100 ℃ for 5min, and finally taking the mould to further form the microporous titanium layer b with the aperture of 10 mu m on the surface of the macroporous titanium layer so as to obtain the multi-shaped water electrolysis electrode plate (as shown in figures 2-5).
The structure of the mold is shown in fig. 1, and the mold comprises a trapezoidal flow field mold opening 1, a functional area flow field mold opening 2 and a rectangular flow field mold opening 3. The trapezoidal flow field die opening 1 is of a plurality of trapezoidal groove structures which are arranged in parallel, the flow field structure of the bipolar plate is in a trapezoidal flow channel structure through die printing, a trapezoidal flow channel ridge 4-2 and a corresponding trapezoidal flow field groove 4 are formed, the trapezoidal bottom edge of the trapezoidal flow channel structure is close to the high alloy steel plate, the groove bottom of the trapezoidal flow channel groove is formed, the trapezoidal top edge is far away from the high alloy steel plate, and the trapezoidal flow field opening 4-1 of the trapezoidal flow channel groove is formed. The rectangular flow field mold opening 3 is a rectangular groove structure with a plurality of parallel arrangement, the flow field structure of the bipolar plate is in a rectangular flow channel structure through mold printing, and a rectangular flow field groove 5 and a rectangular flow channel ridge 6 are formed. The functional area flow field mold opening 2 is positioned between the trapezoidal flow field mold opening 1 and the rectangular flow field mold opening 3, is of a plurality of hollow structures which are regularly and alternately ordered, and forms an array cylindrical functional area 2-1 (used for gas turbulence) between the rectangular flow channel and the trapezoidal flow channel of the bipolar plate through mold printing. The groove structure of the rectangular flow passage is parallel to the groove structure of the trapezoidal flow passage and corresponds to the groove structure of the rectangular flow passage in position, and the corresponding rectangular flow passage groove is communicated with the trapezoidal flow passage groove in position and corresponds to the material inlet and the material outlet.
A trapezoidal flow field injection port 1-1 is arranged on a trapezoidal flow field die opening 1 of the die, and a rectangular flow field injection port 3-1 is arranged on a rectangular flow field die opening 3 of the die. And (3) placing the mould on the polar plate, injecting slurry through the trapezoidal flow field injection port or the rectangular flow field injection port, and forming the flow field structure after treatment. When the microporous titanium layer b with the trapezoidal flow field structure is prepared, the size of the trapezoidal flow field mold side of the adopted mold is correspondingly adjusted, so that the side with the trapezoidal flow field structure on the obtained bipolar plate is ensured to be in an integral trapezoidal shape.
The contact resistance of the prepared polar plate is 0.5m omega cm through testing 2 The corrosion current density is 2.5 mu A/cm 2 As shown in table 1, the power output performance was excellent.
Example 2
Preparing the slurry of the macroporous titanium layer: 30g of spherical atomized titanium powder with the particle size of 75 mu m, 58g of absolute ethyl alcohol, 6g of polyvinyl butyral resin, 3.5g of ammonium bicarbonate and 1.5g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Preparing a microporous titanium layer b slurry: 70g of spherical atomized titanium powder with the particle size of 35 mu m, 20g of absolute ethyl alcohol, 3.5g of polyvinyl butyral resin and 1.5g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Cutting a piece of high alloy steel with the Ti alloy mass content of 10% and the thickness of 0.5mm and the area of 20cm x 10cm, grinding and polishing step by using 200-500-mesh abrasive paper, then putting the high alloy steel plate into an acetone solution, ultrasonically cleaning for 3 times, cleaning for 10min each time, then cleaning by using ultrapure water, and taking out and drying.
Putting the cleaned high-alloy steel plate on a plasma spraying platform, and setting the condition of a spraying machine to be that the plasma enthalpy is 36MJ/kg; the spraying speed is 800mm/s; the spraying temperature is 175 ℃, and spherical dehydrotitanium powder with the grain diameter of 60 mu m is sprayed on the surface of the high alloy steel to form a micropore titanium layer a with the thickness of 0.4mm, and the aperture of the micropore titanium layer a is 100nm. And then placing the mold on the surface of the high alloy steel, printing the macroporous titanium layer slurry on the surface of the microporous titanium layer a according to the shape of the mold, wherein the thickness is 0.4mm, then placing the microporous titanium layer slurry into a 125 ℃ oven for heat treatment for 4min, taking out the microporous titanium layer slurry after the time is up, placing the microporous titanium layer slurry into a-0.5 MPa vacuum furnace, wherein the temperature is 950 ℃, the time is 60min, the argon protection flow is 50mL/min, and taking out the microporous titanium layer slurry after the time is up to obtain the metal substrate with the macroporous titanium layer with the aperture of 12 microns. And then placing a mould on the surface of the macroporous titanium layer, printing the slurry of the microporous titanium layer b to the surface of the macroporous titanium layer along the shape of the mould with the thickness of 0.4mm, drying again at the temperature of 125 ℃ for 4min, and finally taking the mould to further form the microporous titanium layer b with the aperture of 100nm on the surface of the macroporous titanium layer, thereby obtaining the multi-shaped water electrolysis electrode plate. The mold structure was the same as in example 1.
The prepared water electrolysis pole plate has a multi-layer structure, a titanium layer is printed on the high alloy steel, and the contact resistance of the pole plate is only 0.53m omega cm after being tested 2 The corrosion current density is 2.57 mu A/cm 2 Therefore, the prepared plate has excellent output and performance in both performance and durability.
Example 3
Preparing the slurry of the macroporous titanium layer: 40g of spherical atomized titanium powder with the particle size of 100 mu m, 52g of absolute ethyl alcohol, 2g of polyvinyl butyral resin, 3g of ammonium bicarbonate and 1g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Preparing a microporous titanium layer b slurry: 80g of spherical atomized titanium powder with the particle size of 50 mu m, 15g of absolute ethyl alcohol, 3g of polyvinyl butyral resin and 1g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Cutting a piece of high alloy steel with the thickness of 0.5mm and the mass content of Ni alloy of 20cm x 10cm and the area of 30%, grinding and polishing step by using sand paper with 200-500 meshes, then putting the high alloy steel plate into an acetone solution, carrying out ultrasonic cleaning for 3 times, carrying out cleaning for 10min each time, then cleaning with ultrapure water, and taking out and drying.
Putting the cleaned high-alloy steel plate on a plasma spraying platform, and setting the condition of a spraying machine to be that the plasma enthalpy is 50MJ/kg; the spraying speed is 1000mm/s; the spraying temperature is 200 ℃, and the spherical dehydrotitanium powder with the grain diameter of 100 mu m is sprayed on the surface of the high alloy steel to form a micropore titanium layer a with the thickness of 0.4mm, wherein the aperture of the micropore titanium layer a is 10 mu m. And then placing the mold on the surface of the high alloy steel, printing the macroporous titanium layer slurry on the surface of the microporous titanium layer a according to the shape of the mold, wherein the thickness is 0.5mm, then placing the microporous titanium layer slurry into a 150 ℃ oven for heat treatment for 3min, taking out the microporous titanium layer slurry after the time is up, placing the microporous titanium layer slurry into a-0.9 MPa vacuum furnace, carrying out the heat treatment at 600 ℃ for 100min, carrying out argon protection flow of 100mL/min, and taking out the microporous titanium layer slurry after the time is up to obtain the metal substrate with the macroporous titanium layer with the aperture of 50 microns. And then placing a mould on the surface of the macroporous titanium layer, printing the slurry of the microporous titanium layer b to the surface of the macroporous titanium layer along the shape of the mould with the thickness of 0.5mm, drying again at the temperature of 150 ℃ for 3min, and finally taking the mould to further form the microporous titanium layer b with the aperture of 10 mu m on the surface of the macroporous titanium layer so as to obtain the multi-shaped water electrolysis electrode plate. The mold structure was the same as in example 1.
The prepared water electrolysis pole plate has a multi-layer structure, a titanium layer is printed on the high alloy steel, and the contact resistance of the pole plate is only 0.57m omega cm after being tested 2 The corrosion current density is 2.59 mu A/cm 2 Therefore, the prepared polar plate has excellent output and performance in both performance and durability.
Example 4
A continuous production line suitable for embodiments 1-3, the production line comprises a ring-shaped guide rail and a driving electric component, the ring-shaped guide rail is provided with a plurality of electrically driven slide blocks so as to simultaneously place a plurality of stainless steel plates for batch transmission, and simultaneously extend the transmission direction of the ring-shaped guide rail, the production line is sequentially provided with a plasma spraying area, a first thickness detection area, a mold printing area, a second thickness detection area and a drying area, the whole continuous production line is intelligently and logically controlled by a CPU control system, the plasma spraying area mainly comprises a plasma spraying machine, the mold printing area mainly comprises a screen printing machine, the first thickness detection area and the second thickness detection area mainly comprise a thickness detector, and the plasma spraying machine, the screen printing machine and the thickness detector are all in circuit connection with the CPU control system so as to realize the controllability of whether a plurality of areas work and the work sequence; the stainless steel plates are sequentially placed on the sliding blocks to be conveyed, and are sequentially subjected to plasma spraying, first thickness detection, screen printing and second thickness detection to be prepared, in the process, according to the actual size requirement of the metal bipolar plate and the thickness detection result, relevant data are recorded in a CPU (central processing unit) system and regulated and controlled in real time, if the size is not met, the stainless steel plates can be circularly conveyed into a corresponding area to be replenished and brushed again, meanwhile, a human station and a mechanical arm station are also arranged at the position of the whole production line, and finally, a user is taken down by the mechanical arm and conveyed into other production lines.
Comparative example 1
Preparing macroporous titanium layer slurry: 20g of spherical atomized titanium powder with the particle size of 50 mu m, 64g of absolute ethyl alcohol, 10g of polyvinyl butyral resin, 4g of ammonium bicarbonate and 2g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Preparing a microporous titanium layer b slurry: 60g of spherical atomized titanium powder with the particle size of 20 mu m, 35g of absolute ethyl alcohol, 4g of polyvinyl butyral resin and 1g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Cutting a piece of high alloy steel with the thickness of 0.5mm and the Mo alloy mass content of 30% and the area of 20cm x 10cm, grinding and polishing step by using 200-500-mesh abrasive paper, then putting the high alloy steel plate into an acetone solution, ultrasonically cleaning for 3 times, cleaning for 10min each time, then cleaning by using ultrapure water, and taking out and drying.
Placing a mould on the surface of high alloy steel, printing the slurry of the macroporous titanium layer on the surface of the high alloy steel plate according to the shape of the mould, wherein the thickness of the slurry is 0.5mm, then placing the high alloy steel plate into a drying oven at 100 ℃ for heat treatment for 5min, taking out the high alloy steel plate after the time is up, placing the high alloy steel plate into a vacuum oven at-0.1 MPa, keeping the temperature of 1300 ℃, keeping the flow of argon gas at 10mL/min, taking out the high alloy steel plate after the time is up, then placing the mould on the surface of the high alloy steel plate, printing the slurry of the microporous titanium layer b to the surface of the plate along the shape of the mould, drying the high alloy steel plate again, keeping the temperature at 100 ℃ for 5min, and finally taking out the mould to obtain the water electrolysis plate with multiple shapes. The mold structure was the same as in example 1.
Because the micro-pore titanium layer a is not plasma sprayed on the high alloy steel plate, the bottom of the groove is not covered by the titanium layer, the contact resistance is high and reaches 3m omega cm 2 The corrosion current density also reaches 5 mu A/cm 2 From the data, the performance of the plate was poor both in terms of output performance and durability.
Comparative example 2
Preparing the slurry of the macroporous titanium layer: 20g of spherical atomized titanium powder with the particle size of 50 mu m, 64g of absolute ethyl alcohol, 10g of polyvinyl butyral resin, 4g of ammonium bicarbonate and 2g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Preparing a microporous titanium layer b slurry: 60g of spherical atomized titanium powder with the particle size of 20 mu m, 35g of absolute ethyl alcohol, 4g of polyvinyl butyral resin and 1g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Cutting a piece of high alloy steel with the Mo alloy content of 10% and the thickness of 0.5mm and the area of 20cm x 10cm, gradually grinding and polishing by using sand paper with 200-500 meshes, then placing the high alloy steel plate into an acetone solution, ultrasonically cleaning for 3 times, cleaning for 10min each time, then cleaning by using ultrapure water, and taking out and drying.
Putting the cleaned high-alloy steel plate on a plasma spraying platform, and setting the condition of a spraying machine to be 22MJ/kg of plasma enthalpy; the spraying speed is 600mm/s; and spraying spherical dehydrotitanium powder with the particle size of 30 microns to the surface of the high alloy steel at the spraying temperature of 150 ℃ to form a microporous titanium layer a, wherein the pore diameter of the microporous titanium layer a is 10 microns. And then placing a mould on the surface of the high alloy steel, printing the macroporous titanium layer slurry on the surface of the microporous titanium layer a according to the shape of the mould, wherein the mould has no multi-shape structure and no functional region at a joint part, only has a rectangular parallel flow field groove structure and has the thickness of 0.5mm, then placing the mould into a 100 ℃ oven for heat treatment for 5min, taking out the mould after the time is up, placing the mould into a-0.1 MPa vacuum furnace, keeping the temperature at 1300 ℃ for 30min, keeping the flow of argon gas at 10mL/min, and taking out the mould after the time is up to obtain the metal pole plate with the macroporous titanium layer with the aperture of 100 mu m. And then placing the mould on the surface of the mould, printing the slurry of the microporous titanium layer b to the surface of the macroporous titanium layer along the shape of the mould, drying again at the temperature of 100 ℃ for 5min, and finally taking the mould to further form the microporous titanium layer b with the aperture of 10 mu m on the surface of the macroporous titanium layer so as to obtain the water electrolysis electrode plate with the parallel flow field.
Comparative example 2 compared with the examples of the present application, the contact resistance of the electrode plate was lower than that of the electrode plate by using the plasma spraying and titanium layer printing methods 2 The output performance is good; assembling the bipolar plate and the membrane electrode into an electrolytic tank, and testing the electrolytic tank at 1500mA cm -2 The voltage is 1.7V, the mass transfer resistance is 200m omega cm 2 (ii) a However, comparative example 2, which did not adopt a composite flow field structure but a parallel flow field structure, was tested at 1500mA cm under the same test conditions using the same membrane electrode as described above and bipolar plate fabricated in this comparative example 2 to assemble an electrolytic cell -2 The lower voltage is 1.98V, and the mass transfer resistance is 500m omega cm 2 Therefore, the bipolar plate prepared by the invention has small mass transfer and transmission resistance, effectively improves the transmission performance of the bipolar plate and improves the output performance of the electrolytic cell. In addition, the comparative example 2 does not adopt a composite flow field structure, but adopts a parallel flow field structure with general durability, and the corrosion current density is 3 muA/cm through testing 2 Comparative example 1 is 20% higher.
Comparative example 3
Preparing macroporous titanium layer slurry: 20g of spherical atomized titanium powder with the particle size of 50 mu m, 64g of absolute ethyl alcohol, 10g of polyvinyl butyral resin, 4g of ammonium bicarbonate and 2g of dioctyl phthalate are weighed in a beaker and stirred uniformly by a mechanical stirrer for later use.
Cutting a piece of high alloy steel with the thickness of 0.5mm and the Mo alloy mass content of 30% and the area of 20cm x 10cm, grinding and polishing step by using 200-500-mesh abrasive paper, then putting the high alloy steel plate into an acetone solution, ultrasonically cleaning for 3 times, cleaning for 10min each time, then cleaning by using ultrapure water, and taking out and drying.
Putting the cleaned high-alloy steel plate on a plasma spraying platform, and setting the condition of a spraying machine to be 22MJ/kg of plasma enthalpy; the spraying speed is 600mm/s; and spraying spherical dehydrotitanium powder with the particle size of 30 microns to the surface of the high alloy steel at the spraying temperature of 150 ℃, then placing a mould on the surface of the high alloy steel, printing the slurry on the surface of the high alloy steel with the thickness of 0.5mm according to the shape of the mould in the embodiment 1, then placing the high alloy steel into a 100 ℃ oven for heat treatment for 5min, and taking out and demoulding after the time is up to obtain the multi-shaped water electrolysis polar plate.
Comparative example 3 in comparison with the examples of the present application, only the macroporous titanium layer paste was printed to form the functional coating. Through tests, on the basis of adopting a plasma spraying high-alloy steel plate and mould printing a macroporous titanium layer, the prepared polar plate has excellent output performance, and the contact resistance is 0.53m omega cm 2 And no multi-layer structure, the water-gas transmission performance in the interior is not excellent in example 1, and the corrosion current density is higher and is 2.78 muA/cm 2 。
TABLE 1 test results
| Serial number | Contact resistance of m omega cm 2 | Corrosion current density muA/cm 2 |
| Example 1 | 0.5 | 2.5 |
| Example 2 | 0.53 | 2.57 |
| Example 3 | 0.57 | 2.59 |
| Comparative example 1 | 3 | 5 |
| Comparative example 2 | 0.59 | 3 |
| Comparative example 3 | 0.53 | 2.78 |
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A bipolar plate for hydrogen production by PEM water electrolysis is characterized in that: the method comprises the following steps of taking an alloy steel plate as a substrate, and sequentially arranging a microporous titanium layer a, a macroporous titanium layer and a microporous titanium layer b on the surface of the substrate;
the pore diameters of the microporous titanium layer a and the microporous titanium layer b are both 100nm-10 microns, and the pore diameter of the macroporous titanium layer is larger than 10 microns and less than or equal to 100 microns;
the microporous titanium layer a at least comprises spherical dehydrotitanium powder, the macroporous titanium layer at least comprises spherical atomized titanium powder with the particle size of 50-100 mu m and a pore-forming agent, and the microporous titanium layer b at least comprises spherical atomized titanium powder with the particle size of 20-50 mu m;
the composite flow field structure of the bipolar plate is formed by the macroporous titanium layer and the microporous titanium layer b, the composite flow field structure comprises a trapezoidal flow channel ridge, a functional area and a rectangular flow channel ridge, the rectangular flow channel ridge is located close to a cathode inlet or an anode inlet and is connected with one side of a material inlet and the functional area, the trapezoidal flow channel ridge is located close to a cathode outlet or an anode outlet and is connected with the other side of the material outlet and the functional area, and the functional area is in an array column shape.
2. The bipolar plate for PEM water electrolysis hydrogen production according to claim 1, wherein: the height of the trapezoidal flow channel ridge and the height of the rectangular flow channel ridge are both 0.3-1mm, the width of the groove bottom of the trapezoidal flow channel is 0.2-0.5mm, the width of the opening of the trapezoidal flow channel is 0.4-1mm, and the width of the groove of the rectangular flow channel is 0.5-1mm.
3. The bipolar plate for PEM water electrolysis hydrogen production according to claim 1, wherein: the thickness of the microporous titanium layer a is 0.1-0.4mm; the thickness of the macroporous titanium layer and the thickness of the microporous titanium layer b are both 0.3-0.5mm.
4. The bipolar plate for PEM water electrolysis hydrogen production according to claim 1, wherein: the particle size of the spherical dehydrogenation titanium powder is 30-100 mu m; the macroporous titanium layer comprises spherical atomized titanium powder with the particle size of 50-100 mu m, a solvent, a binder, a pore-forming agent and a plasticizer; the microporous titanium layer b comprises spherical atomized titanium powder with the particle size of 20-50 mu m, a solvent, a binder and a plasticizer.
5. The bipolar plate for PEM water electrolysis hydrogen production according to claim 4, which is characterized in that: the solvent in the macroporous titanium layer and the microporous titanium layer b is independently at least one of ethanol, toluene or methanol, the binder in the macroporous titanium layer and the microporous titanium layer b is independently at least one of polyvinyl butyral resin or acrylic resin, the plasticizer in the macroporous titanium layer and the microporous titanium layer b is independently at least one of dioctyl phthalate, dibutyl phthalate or propylene glycol diacetate polyester, and the pore-forming agent comprises one or a combination of more than two of urea, ammonium bicarbonate, sodium carbonate and oxalic acid.
6. The bipolar plate for PEM water electrolysis hydrogen production according to claim 4, which is characterized in that: in the macroporous titanium layer, the mass ratio of spherical atomized titanium powder, a solvent, a binder, a pore-forming agent and a plasticizer is 20-40:52-64:2-10:3-4:1-2; in the microporous titanium layer b, the mass ratio of spherical atomized titanium powder, solvent, binder and plasticizer is 60-80:15-35:3-4:1-2.
7. The bipolar plate for PEM water electrolysis hydrogen production according to claim 1, wherein: the thickness of the alloy steel plate is 0.5-1mm, the alloy steel plate contains one or more of Ni, ti and Mo alloy elements, and the mass content of the total alloy elements is 10-30 wt.%.
8. A method for preparing the bipolar plate for PEM water electrolysis hydrogen production as defined in any one of claims 1-7, wherein: comprises the following steps:
(1) Preparing macroporous titanium layer slurry: stirring and mixing spherical atomized titanium powder with the particle size of 50-100 mu m with a solvent, a binder, a pore-forming agent and a plasticizer to obtain macroporous titanium layer slurry;
preparing a microporous titanium layer b slurry: stirring and mixing spherical atomized titanium powder with the particle size of 20-50 mu m with a solvent, a binder and a plasticizer to obtain slurry of the microporous titanium layer b;
(2) Pretreating an alloy steel plate;
(3) Spraying spherical dehydrotitanium powder to the surface of the alloy steel plate obtained by pretreatment in a plasma spraying mode to form a microporous titanium layer a;
(4) Printing the macroporous titanium layer slurry on the microporous titanium layer a in a mould printing mode, and drying and demoulding;
(5) Transferring to a vacuum furnace, and carrying out temperature programming sintering to prepare a metal pole plate with a macroporous titanium layer;
(6) And printing the slurry of the microporous titanium layer b onto the macroporous titanium layer by adopting a mould printing mode, drying and demoulding to form the microporous titanium layer b on the surface of the macroporous titanium layer, thus preparing the water electrolysis bipolar plate.
9. The method for preparing the bipolar plate for PEM water electrolysis hydrogen production according to claim 8, characterized in that: the plasma spraying conditions are as follows: the enthalpy of the plasma is 22-50MJ/kg; the spraying speed is 600-1000mm/s; the spraying temperature is 150-200 ℃;
the conditions of the temperature programming in the step (5) are as follows: argon protection flow: 10-100mL/min, vacuum: -0.1 to-0.9 MPa, time: 30-100min; the heating rate is as follows: 5-20 ℃/min;
the roasting temperature is 600-1300 ℃;
the drying temperature is 100-150 ℃;
the pretreatment of the alloy steel plate comprises the following steps: and (3) polishing, polishing and cleaning the surface of the alloy steel plate, then putting the alloy steel plate into an acetone solution for ultrasonic cleaning, taking the alloy steel plate out, using ultrapure water for ultrasonic cleaning, taking the alloy steel plate out, and blow-drying the alloy steel plate for later use.
10. The method for preparing the bipolar plate for PEM water electrolysis hydrogen production according to claim 8, characterized in that: the steps (3) - (4) are completed by adopting a continuous production line with an annular guide rail, a plurality of electrically driven sliding blocks are arranged on the annular guide rail, and stainless steel plates are placed on the sliding blocks; be equipped with plasma spraying district, thickness detection district, mould printing district, no. two thickness detection districts on the line is produced to the continuous type in proper order, ring rail and the line is produced to the continuous type all with control system circuit connection.
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| CN202211538214.5A CN115852411A (en) | 2022-12-01 | 2022-12-01 | Bipolar plate for hydrogen production by PEM water electrolysis and preparation method thereof |
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| CN202211538214.5A CN115852411A (en) | 2022-12-01 | 2022-12-01 | Bipolar plate for hydrogen production by PEM water electrolysis and preparation method thereof |
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