The present disclosure relates to an electrolyzer, and in particular to a membrane-less electrolyzer.
Membrane-less electrolyzers utilize fluidic forces instead of membranes or separators for the separation of the electrolysis gas products. These electrolyzers have low ionic resistance, simple design, and ability to work with electrolytes at different pH values. However, the interelectrode distance and the flow velocity should be large at high production rates in order to prevent gas cross over. The ionic resistance is higher at larger interelectrode distances and the required pumping power increases by the flow velocity.
Renewable energies are being developed as a clean source of energy to substitute fossil fuels. However, the sources of renewable energies are intermittent. The surplus energy of renewables can be stored in the form of hydrogen using water electrolysis when the renewable sources are available. Furthermore, hydrogen produced from water electrolysis is a clean alternative to fossil fuels for the transportation which reduces the air pollutant emissions from vehicles [1, 2]. Hydrogen from water electrolysis can reach high purities [3]. High purity hydrogen can be used directly in fuel cells to produce energy for the vehicles or compensation of the shortage of energy from renewable sources at the energy peak demand. Hydrogen production from water electrolysis has been considered an expensive process [4]. The design, efficiency, and throughput of water electrolyzers determine the cost of hydrogen production. Therefore, it is necessary to improve the performance of the electrolyzers.
The main water electrolysis methods are alkaline electrolyzers and polymer electrolyte membrane (PEM) electrolyzers that are available commercially, and anion exchange membrane (AEM) electrolyzers, solid oxide electrolyzers (SOE), and membrane-less electrolyzers that are in the development and research stage [3, 5, 6].
Alkaline electrolyzers work with basic electrolytes [7]. The electrodes of alkaline electrolyzers are separated by a diaphragm in order to prevent gas cross-contamination [8]. Alkaline electrolyzers are the most commercially used technologies for hydrogen production due to their simple design and inexpensive catalyst materials [8]. PEM electrolyzers use a membrane coated by catalysts on both sides [9]. This membrane allows the protons migration but prevents the gas cross over [10]. PEM electrolyzers can be used at high current densities, they have low gas cross over, and they are compact [9]. AEM electrolyzers work with alkaline electrolytes and use an anion conductive membrane [11]. This technology can reduce the capital cost of electrolyzers due to the usage of non-precious metal electrodes [12]. SOEs use a solid electrolyte with two porous electrodes on the two sides of this electrolyte [13]. These electrolyzers have higher efficiency since they are operating at high temperatures [14]. However, the solid electrolyte and the electrodes should be chemically stable in the highly oxidizing and reducing environments [13].
The above-mentioned electrolyzers use a membrane or a diaphragm to prevent the gas cross-contamination. Membrane-less electrolyzers have been introduced to remove the need for the membranes [15]. Membrane-less electrolyzers rely on the fluidic flow [15-19], buoyancy forces [20], or surface forces for the gas product separation. Removing the membrane simplifies the design of the electrolyzer, reduces the electrolyzer cost, and increases the lifetime and durability of the device [5]. Furthermore, a membrane-less electrolyzer is compatible with a wide range of electrolytes at different PH [15]. Thus, it can be used for various electrochemical reactions such as water electrolysis for hydrogen production and brine electrolysis for chlorine production without significant modification in its design [16, 22].
The membrane-less electrolyzers geometry can be classified based on the electrode configuration into parallel [15, 16] and mesh electrodes [17-19]. In the parallel electrode electrolyzer (PE electrolyzer), the electrodes are at the two opposites sides of a rectangular channel. The liquid is flowing between the electrodes. Gas products are flowing in between the electrodes until the end of the channel. The liquid flow keeps the bubbles at the channel sides to prevent cross over. The volume fraction of bubbles increases by going downstream. Therefore, the channel length and the flow rate should be decided carefully to prevent the formation of bubbles larger than half of the channel width.
The mesh electrodes geometry is made of two plane meshes that act as catalysts. The liquid flow enters the area between the meshes and flows through the pores of the mesh. The bubbles are formed on the surface of the mesh and they move to the outer side of the mesh after the detachment. The mesh electrodes electrolyzer can achieve higher production rate compared to the PE electrolyzer as the bubbles go through the mesh pores and leave the interelectrode region faster. An equal velocity in all pores of the mesh is necessary for removing the growing bubbles at all positions of the mesh. Furthermore, the bubbles growing on the inner side of the mesh should detach at sizes smaller than the mesh pore size in order to allow the bubbles to flow through the mesh.
The product separation is a challenge for the membrane-less electrolyzers due to the absence of the membrane or separator. The bubble growth at the electrode and movement in the channel are being investigated in order to overcome this challenge [23-25]. The bubble coalescence and large bubble detachment from the electrodes can lead to the formation of bubbles larger than half of the channel width which leads to gas cross over. Besides, the large bubble formation is more frequent at high production rates. Consequently, the gas cross over is higher at higher production rates.
Enlarging the space between the electrodes leads to higher maximum production rate, but it imposes additional ohmic losses due to the longer interelectrode distance. Moreover, bubbles moving between electrodes block ionic pathways that adds to the overpotential losses [26].
In mesh electrode electrolyzers, however, bubbles larger than the pores cannot go through the pores easily and they flow between the electrodes until the end of the channel which limits the production rate.
It is thus a goal of the present disclosure to address the above-mentioned inconveniencies.
The present invention addresses the above-mentioned limitations by providing an electrolyzer according to claim 1.
The membrane-less electrolyzer of the present disclosure increases the throughput of the electrolyzer without having to increase the interelectrode distance and flow velocity. The electrolyzer may have, for example, three channels separated by porous walls. The electrolyte enters, for example, a middle channel and flows to the outer channels through the wall pores. The gas products are, for example, produced in the outer channels. Results show Hydrogen cross over to be as low as 0.14±0.06% in this electrolyzer at Re=109 and j=300 mA/cm3. This cross over is 58 times lower than hydrogen cross over in an equivalent membrane-less electrolyzer with parallel electrodes under the same working conditions.
The electrolyzer of the present disclosure allows the production rate to be improved by adding pores to the wall of PE electrolyzers and generating bubbles in the outer sides of the interelectrode region. Producing bubbles outside the interelectrode region resolves the production rate limitation in known electrolyzers. Moreover, by doing so, the overpotential due to the bubble movement between electrodes decreases and, in addition, the electrodes distance can be decreased.
Another aspect of the present disclosure concerns a device assembly comprising a plurality of electrolyzers.
Yet another aspect of the present disclosure concerns an electrolysis method according to claim 43 and a method for operating an electrolyzer according to claim 46.
Moreover, the addition of, for example, heptadecafluorooctancesulfonic acid potassium (PFOS) as a surfactant to the electrolyte is shown to further reduce the hydrogen cross over to 0.11±0.05% and the overpotential by 1.9% at Re=109 and j=300 mA/cm3.
Modification of electrolyte properties with surfactant reduces the size of bubbles. The addition of the surfactant to the electrolyte decreases the surface tension. The bubble detachment size is smaller when the surface tension is lower. Furthermore, the surfactant molecules adsorbed to the interface of the bubble prevent the bubble coalescence. Therefore, the surfactant improves the production throughput of the electrolyzer. In an electrolyte with the surfactant, the bubbles detach faster from the electrode surface. This fast bubble detachment reduces the electrode surface coverage by the bubbles and decreases the corresponding ohmic losses.
The surfactant enhances the production rate and product separation in membrane-less electrolyzers, but the production rate cannot be increased further when the space between the electrodes is filled with bubbles, a limitation which is resolved by the electrolyzer of the present disclosure. The electrolyzer of the present disclosure combined with the surfactant thus can assure a significant increase in production rate while assuring low cross over.
Other advantageous features can be found in the dependent claims.
The above and other objects, features and advantages of the present invention and the manner of realizing them will become more apparent, and the invention itself will best be understood from a study of the following description with reference to the attached drawings showing some preferred embodiments of the invention.
Herein, identical reference numerals are used, where possible, to designate identical elements that are common to the Figures.
The electrolyzer 1 is, for example, a membrane-less electrolyzer or a porous wall PW electrolyzer.
The electrolyzer 1 may comprise at least a first electrode 3 and at least a second electrode 5 for carrying out electrolysis. The electrolyzer 1 may also comprise a first fluidic channel 7 configured to receive an electrolyte EL, a second fluidic channel 9 configured to receive the electrolyte EL from the first fluidic channel 7 and a third fluidic channel 11 configured to receive the electrolyte EL from the first fluidic channel 7.
The second fluidic channel 9 includes, for example, the first electrode 3 and the third fluidic channel 11 includes, for example, the second electrode 5. The first fluidic channel 7 may, for example, be electrode-free or electrode-less.
The first fluidic channel 7 is in fluidic communication with the second and third fluidic channels 9, 11. The first fluidic channel 7 may, for example, be located between or enclosed by the second and third fluidic channels 9, 11. The first fluidic channel 7 may, for example, be located above the second and third fluidic channels 9, 11.
The first fluidic channel 7 is connected to the second and third fluidic channels 9, 11 via a plurality of fluidic canals 15 extending from the first fluidic channel 7 to each of the second and third fluidic channels 9, 11.
The first fluidic channel 7 is connected to each of the second and third fluidic channels 9, 11 via a plurality of inclined fluidic canals 15.
The plurality of fluidic canals 15 are distributed or spaced apart along a direction of extension (or along the length (L)) of the first fluidic channel 7 to provide the electrolyte EL to each of the second and third fluidic channels 9, 11 in a distributed manner along a direction of extension (or along the length (L)) of the second and third fluidic channels 9, 11.
The exemplary embodiment of
The first fluidic channel 7 is, for example, configured to provide the electrolyte EL directly via fluidic canals 15 to both the second and third fluidic channels 9, 11. The first fluidic channel 7 is, for example, configured to provide the electrolyte EL simultaneously, via fluidic canals 15, to both the second and third fluidic channels 9, 11.
The first fluidic channel 7 comprises or consists of a plurality of stacked or superposed (substantially) Y-shaped sections SY or partial Y-shaped sections SY (see, for example,
The fluidic canals 15 are, for example, inclined fluidic canals. Each fluidic canal 15 may be an inclined fluidic canal, or a subset or part of the plurality of fluidic canals 15 may be inclined fluidic canals.
The inclined fluidic canals 15 are, for example, inclined with respect to the first fluidic channel 7 in a direction non-perpendicular to an electrolyte flow direction F through the first fluidic channel 7.
The inclined fluidic canals 15 are inclined with respect to the first 7, second 9 or third 11 fluidic channels. The inclined fluidic canals 15 are preferably inclined with respect to each of the first 7, second 9 and third 11 fluidic channels.
The inclined fluidic canals 15 define, for example, an angle α with respect to the first fluidic channel 7. The angle α is, for example, not equal to 90°. The angle α is, for example, an acute angle.
The inclined fluidic canals 15 define an angle β with respect to the second fluidic channel 9 and an angle δ with respect to the third fluidic channel 11. The angles β and δ are, for example, not equal to 90°. The angles β and δ are, for example, acute angles.
Each inclined fluidic canal 15 may define angles β and δ between 10° and 80°, or between 20° and 70°, or between 30° and 60° with respect to the second fluidic channel 9 or with respect to the third fluidic channel 11.
Each inclined fluidic canal 15 may define an angle α between 10° and 80°, or between 20° and 70°, or between 30° and 60° with respect to first fluidic channel 7.
The inclined fluidic canals 15 are, for example, inclined with respect to the first fluidic channel 7 in a direction non-perpendicular to an electrolyte flow direction F through the first fluidic channel 7.
The first fluidic channel 7 is interconnected to the second and third fluidic channels 9, 11 via the plurality of inclined fluidic canals 15. The plurality of inclined fluidic canals 15 may be separated by pillars 25 consisting of or comprising solid material. Alternatively, in an alternative non-limiting exemplary embodiment, the fluidic canals 15 may be, for example, suspended in air or in suspension between the first fluidic channel 7 and the second and third fluidic channels 9, 11.
The plurality of inclined fluidic canals 15, or a subset thereof, extends for example outwards and away from the first fluidic channel 7, or outwards and away from the first fluidic channel 7 and away from each other.
The inclined fluidic canals may extend outwards and away from the first fluidic channel 7 and extend in a direction of electrolyte flow F through the first fluidic channel 7 or membrane-less electrolyzer 1.
Each fluidic canal 15 extends from the first fluidic channel 7 to the second and third fluidic channels 9, 11 to each connect physically with or to a different part of the second and third fluidic channels 9, 11.
Each fluidic canal 15 includes a passage PS15 through which the electrolyte passes from the first fluidic channel 7 to the second and/or third fluidic channels 9, 11. 10. The fluidic canal 15 includes at least one partition 17 defining the passage PS15 through which the electrolyte flows from the first fluidic channel 7 to the second and/or third fluidic channel 9, 11. The partition 17 extends between the first fluidic channel 7 and the second 9 and/or third 11 fluidic channel.
The first, second and third fluidic channels 7, 9, 11 each include a porous wall permitting fluidic communication between the first, second and third fluidic channels. The first 7, second 9 and third 11 fluidic channels each include at least one wall SW7, SW9, SW11 each defining a plurality of apertures or pores P7, P9, P11. Each fluidic canal 15 may extend between an aperture or pore P7 of the first fluidic channel 7 and an aperture or pore P9, P11 of the second or third fluidic channel 9, 11.
As mentioned, the first fluidic channel 7 may, for example, be located between the second and third fluidic channels 9, 11. A portion SW7A of the porous wall SW7 of the first fluidic channel 7 located and extending opposite the second fluidic channel 9 and a portion SW7B of the porous wall SW7 of the first fluidic channel 7 located and extending opposite the third fluidic channel 11 extend non-parallel with respect to each other, or extend inclined at an angle with respect to a central axis CA to distribute the electrolyte EL (substantially) equally in the fluidic canals 15 that are distributed along the first fluidic channel 7. The central axis CA can for, example, be located at the geometrical center.
The inclination with respect to the central axis CA is, for example, at an angle of less than 5, or 4, or 3, or 2 or 1 degree to distribute the electrolyte equally in the fluidic canals (15).
Each fluidic channel 7, 9, 11 includes or defines a passage PS7, PS9, PS11 through which the electrolyte flows inside the electrolyzer 1.
In a non-limiting exemplary embodiment, the second fluidic channel 9 and/or the third fluidic channel 11 may comprise first and second side walls SW1, SW2 (see, for example,
The first or second side wall SW1, SW2 may include the first or second electrodes 3, 5. In a non-limiting exemplary embodiment shown in
The second and the third fluidic channels 9, 11 may, for example, include electrodes E3, E5 inside the second and the third fluidic channels 9, 11 and on an outer wall or an outer wall section of the second and the third fluidic channels 9, 11. The outer electrodes E3, E5 may, for example, be located on the first side walls SW1 of the second and the third fluidic channels 9, 11.
Similarly, the first fluidic channel 7 (see, for example,
The fluidic channels 7, 9, 11 and the fluidic canals 15 may, however, define different cross-sectional profiles for the passages PS7, PS9, PS11 and PS15 and not necessarily a rectangular profile shown in the exemplary embodiment of
The first electrode 3 is, for example, located on the at least one wall SW9 of the second fluidic channel 9 and the second electrode 5 is, for example, located on the at least one wall SW11 of the third fluidic channel 11.
The electrodes may, for example, be non-porous electrodes or non-mesh electrodes. The fluidic canals 15 are, for example, electrode-less.
The first and second electrodes 3, 5 may, for example, include a plurality of apertures or pores PEL3, PEL5 extending through the first and second electrodes 3, 5 and communicating with the plurality of apertures or pores P9, P11 defined by the at least one wall SW9, SW11 of the second and third fluidic channels 9, 11. The plurality of apertures or pores PEL3, PEL5 in the first and second electrodes 3, 5 may, for example, be aligned or symmetrically located opposite one another, as shown for example in
The apertures or each aperture or pore P7 of the first fluidic channel 7 and/or the apertures or each aperture or pore P9 the second fluidic channel 9 and/or the apertures or each aperture or pore P11 of the third fluidic channel 11 may have an opening width (W) or diameter between 50 μm and 200 μm, or between 60 μm and 180 μm, or between 80 μm and 160 μm.
The fluidic canals 15 or each fluidic canal 15 may, for example, define an opening width (W) or diameter between 50 μm and 200 μm, or between 60 μm and 180 μm, or between 80 μm and 160 μm. The passages PS15 of the fluidic canals 15 may also, for example, define opening widths or diameters of such values. The plurality of apertures or pores PEL3, PEL5 extending through the first and second electrodes 3,5 may similarly define, for example, opening widths or diameters of such values.
Alternatively, the plurality of apertures or pores PEL3, PEL5 extending through the first and second electrodes 3,5 may define openings larger in width (W) or diameter than the openings defined by the pores or apertures P9, P11 of the first or second fluidic channels 9, 11, for example, between 10% and 90% greater.
The apertures or pores PEL3, PEL5 extending through the first and second electrodes 3, 5 may, for example, tapered or curved inwards at the extremity of the aperture or pore PEL3, PEL5, and tapered or curved inwards towards the supporting wall upon which the electrode is attached. This assures a smoother displacement of the electrolyte and bubbles and the easier detachment of bubbles.
The internal width (W) or diameter of the first fluidic channel 7 and/or second fluidic channel 9 and/or third fluidic channel 11 may, for example, be greater than the opening defined by the pores or apertures P7, P9, P11 of the first, second, or third fluidic channels 7, 9, 11. The internal width (W) or diameter may, for example, be between 10% and 200% greater. The internal width (W) or diameter may, for example, be between 55 μm and 600 μm. The internal height (H) may, for example, also be between 10% and 200% greater. The internal height (H) may, for example, be between 55 μm and 600 μm.
The length (L) of the first fluidic channel 7 and/or second fluidic channel 9 and/or third fluidic channel 11 may, for example, be between 5 mm and 50 mm. The length (L) of the fluidic canals 15 may, for example, be between 50 μm and 500 μm, for example 200 μm.
The fluidic channels, 7, 9, 11 may, for example, define micro-fluidic channels in cross-section. The fluidic canals 15 may define micro-fluidic canals in cross-section.
It is, however, noted that these values are provided as non-limiting and exemplary values.
An internal and/or external width (W) or diameter of the first fluidic channel 7, may, for example, be tapered, for example, tapered along the length (L) of the first fluidic channel 7. The internal and/or external width (W) or diameter reduces in the direction of extension from an inlet 21 to outlets 23A, 23B. The reduction from one end of the of the first fluidic channel 7 to an opposite end of the first fluidic channel 7 may, for example, be between 5% and 35%, for example, 25%. This assures a uniform distribution of the electrolyte to the outer fluidic channels for electrolysis.
The first fluidic channel 7 includes an input section IS configured to input the electrolyte, the input section IS including the inlet 21 through which the electrolyte EL is inserted into the electrolyzer 1. The first fluidic channel 7 or electrolyzer 1 also includes an output section OS consisting of or comprising, for example, a plurality of inclined fluidic canals 15 and a V-shaped abutment or stop 27.
The second 9 and third 11 fluidic channels may, for example, also include inlets 21A and 21B (for example, a first lateral inlet 21A and a second lateral inlet 21B) to remove the bubbles faster from the second 9 and third 11 fluidic channels. The liquid velocity at inlets 21A and 21B can, for example, be different since the number of bubbles in the hydrogen side, for example, the second fluidic channel 9 is twice the number of bubbles in the oxygen side, for example, the third fluidic channel 11.
The inlets 21A and 21B are attached to and in fluid communication with the second 9 and third 11 fluidic channels.
The first 7, second 9 and third 11 fluidic channels are closed or partially closed fluidic channels. The electrolyzer 1 may, for example, comprise a lid 31 configured to close the first, second and third fluidic channels 7, 9, 11.
The electrolyzer 1 may further include a pump (not shown) for pumping the electrolyte EL into the first fluidic channel 7 and through the fluidic canals 15, as well as through the second and third fluidic channels 9, 11 and out of the electrolyzer 1 via the outlets 23A, 23B for accessing products generated by the membrane-less electrolyzer. The pump may, for example, be connected to the inlet 21 and connected thereto, for example, directly or indirectly via tubing.
The electrolyzer 1 may also include electrical connection wires or lines 33 in electrical connection with the first and second electrodes 3, 5 and configured to be connected or connected to an electrical energy source (for example, a solar cell) for providing electrical energy (current, voltage) to the first and second electrodes 3,5 to carry out the electrolysis. The first electrode 3 may for example define a cathode and the second electrode 5 may for example define an anode.
An electrolyte EL is provided to the inlet 21 and the first fluidic channel 7 is configured to distribute the electrolyte EL to the second and third fluidic channels 9, 11, via the inclined fluidic canals 15 and the second and third fluidic channels 9,11 are configured to generate products for output via the electrical energy provided to the electrodes 3, 5 of the second and third fluidic channels 9,11.
The electrolyte may, for example, comprises or consists of water and the generated products comprise or consist of Hydrogen and Oxygen. However, the electrolyzer 1 of the present disclosure is not limited to such an electrolyte and output gases and these are solely provided as a non-limiting example in the present description and in the Figures. For example, the electrolyzer 1 may be used for brine electrolysis for chlorine production.
The present disclosure also concerns a device assembly comprising a plurality of membrane-less electrolyzers 1.
The electrolyzer 1 or porous wall electrolyzer 1 (PW electrolyzer) shown in
The performance of a PW electrolyzer 1 can be improved further by using a surfactant in the electrolyte EL.
Accordingly, the present disclosure also concerns an electrolysis method comprising the steps of providing the membrane-less electrolyzer 1 and providing an electrolyte EL and a surfactant into the membrane-less electrolyzer 1 to carry out electrolysis. The surfactant may comprise or consist solely of heptadecafluorooctancesulfonic acid potassium (PFOS). Electrolysis is, for example, carried out to produce Hydrogen and Oxygen with an electrolyte comprising or consisting solely of water.
The present disclosure also concerns a method for operating an electrolyzer comprising the steps of providing a membrane-less electrolyzer 1 and providing the electrolyte EL to the first or middle fluidic channel 7 of the membrane-less electrolyzer 1 for distribution to the outer fluidic channels 9, 11 to carry out electrolysis. The electrolyte EL is provided simultaneously to the second and third fluidic channels and circulated through the second and third fluidic channels to extract or carry the generated (gas) products to the electrolyzer 1 outlets 23A, 23B. The electrolyte EL may be provided with a surfactant. The surfactant may comprise or consist solely of heptadecafluorooctancesulfonic acid potassium (PFOS). Electrolysis may for example be carried out to produce Hydrogen and Oxygen.
The Inventors compared the product purity and the performance of the PW electrolyzer 1 with a parallel-electrode electrolyzer (PE electrolyzer). This comparison demonstrates the effectiveness of the porous walls. The present disclosure provides guidelines for the design of membrane-less electrolyzers 1 for achieving, for example, high throughput production of hydrogen with high purity.
The PE and the PW electrolyzers shown in
Decreasing the production rate is one approach to reduce the bubbles' size and cross over.
Adding a surfactant to the electrolyte is another solution for reducing the bubbles' size. Heptadecafluorooctancesulfonic acid potassium (PFOS) is used as the surfactant in 1 M sulfuric acid.
One goal of the PW electrolyzer 1 design is to reduce the gas cross over. There are two porous walls between nucleation sites in the PW electrolyzer 1 that helps the product separation. The bubbles cannot go through the wall pores due to the opposite flow direction from the middle channel 7. Furthermore, a bubble reaches the minimum energy in the spherical shape. Consequently, the large bubbles flow in the outer channels 9, 11 rather than going through the wall pores as these bubbles deform less in the outer channels 9, 11. A confined bubble travels in the outer channel 9, 11 rather than the wall pores as it experiences smaller deformation. As a result, this design can efficiently separate the large bubbles that are forming at high current densities. However, smaller bubbles can flow through the wall pores and move to the middle channel 7. This happens especially when there is a reverse flow in the wall pores. Moreover, the ionic resistance between the electrodes 3,5 is directly proportional to the size of wall pores. Therefore, this design is preferably optimized in order to achieve good product separation and minimize the ionic resistance.
Two exemplary design criteria of the PW electrolyzer 1 are an equal distribution of liquid flow in the wall pores and minimum gas cross over. The numerical simulations are carried out using, for example, ANSYS Fluent software from ANSYS Inc to optimize the design.
Secondly, mixture equations are solved to estimate the gas cross over in each geometry. The primary phase is water and the secondary phases are hydrogen and oxygen. The water enters from the bottom of the device at the velocity of 0.4 m/s and exits through the outer channels' outlets. Hydrogen and oxygen enter the channel through small inlets on the outer sides of posts at the velocities of 0.02 m/s and 0.01 m/s, respectively. The boundary conditions are shown in
The maximum velocity along the wall pores are drawn in
Geometry 1 has canals/pores 15 with 100 μm length. The liquid flow velocity is not equal in the pores of this design and the water volume fraction is less than 0.8 in the centerline. The length of canal/pores 15 is increased from 100 μm in Geometry 1 to 200 μm in Geometry 2. This change increases the water volume fraction to 0.93 at the centerline. However, the flow distribution is not uniform in the canals/pores 15. The porous walls are rotated by 0.75° in the opposite direction to construct Geometry 3. The flow distribution is uniform and the water volume fraction is 0.99 in Geometry 3.
The bubble generation after adding the PFOS surfactant to the electrolyte EL is shown in
The crossover of hydrogen to the oxygen side in the PW electrolyzer 1 is shown in
A comparison of
The present disclosure shows that successful product separation is a challenging task in the membrane-less electrolyzers at high current densities. This disclosure describes geometry modification and the addition of surfactant to the electrolyte as two strategies and solutions that facilitate product separation. A PE electrolyzer achieves good product separation at a low current density of 75 mA/cm2 and Re=109. However, the hydrogen cross over becomes more than the flammability limit at a higher current density of 300 mA/cm2. The bubble coalescence and large bubble detachment are the main reasons for the formation of large bubbles in the channel that leads to unsafe cross-contamination. The addition of PFOS surfactant to the electrolyte reduces the cross over to the values below the flammability limit at j=300 mA/cm2 as a result of smaller bubble generation and bubble coalescence prevention. Moreover, the PFOS surfactant decreases the surface screening of the electrodes by the bubbles resulting in lower overpotentials.
The geometry of membrane-less electrolyzers can be modified to suppress the cross-contamination of products. The Inventors present PW electrolyzers 1 as an innovative type of membrane-less electrolyzers with an enhanced product separation compared to PE electrolyzers. The PW electrolyzer 1 has a middle channel 7 where the electrolyte EL flows and two outer channels 9, 11 for the product generation. The hydrogen cross over is 58 times smaller in the PW electrolyzer 1 compared to the equivalent PE electrolyzer using 1M H2SO4 at Re=109 and j=300 mA/cm2. A bubble forms in the middle channel 7 of the PW electrolyzer 1 at small Re due to the pressure imbalance imposed by two-phase flows. This bubble forms at the beginning of the PW electrolyzer 1 operation. This bubble grows until the flow reaches the steady-state. Although the bubble in the middle channel 7 does not lead to the cross over, it increases the ionic resistance. The size of this bubble is inversely proportional to the Re and it does not form at Re=109. The PFOS surfactant enhances the electrochemical performance of the PW electrolyzer 1 since the bubbles are not forming in the middle channel 7 and they are not blocking the wall pores/canals 15.
The large-scale membrane-less electrolyzers have a larger interelectrode distance than the microfluidic electrolyzers due to the flow of larger bubbles in the scaled-up electrolyzers. The PW electrolyzer 1 design can be scaled-up without increasing the interelectrode distance since there is no bubble flowing between the electrodes. The fabrication of inclined pores/canals 15 and deposition of catalysts only on one side of the porous walls might be challenging. However, additive manufacturing technologies can be used for the fabrication of large-scale PW electrolyzers [30].
The fabrication of the PW electrolyzer 1 starts by depositing 200 nm titanium on a silicon wafer. The electrical connections are made by doing photolithography and metal ion beam etching on the titanium layer. Afterwards, the porous walls SW2 supporting vertical electrodes 3,5 are made using the SU8 process with a height of 70 μm. Platinum is sputtered on the device followed by ion beam etching [31]. The ion beam etching removes Platinum from the horizontal surfaces but platinum remains on the vertical walls SW2 of SU8. The platinum on the vertical walls SW2 is in contact with titanium on the horizontal floor. Subsequently, the fluidic channels 7, 9, 11 are fabricated in SU8. The height of the fluidic channels 7, 9, 11 is 80 μm. The inner sides of the porous walls are covered with SU8 in this step to define fluidic channel 7. Therefore, platinum is in contact with electrolyte only in the outer channels 9, 11. The inlet 21 and outlets 23A, 23B are punched in a Polydimethylsiloxane PDMS piece. A thin layer of SU8 is coated on this piece.
Next, this PDMS piece is bonded to the device to seal the channels 7, 9, 11 [32].
The PE electrolyzer was fabricated with the same process. The interelectrode distance and electrodes active area of the PE electrolyzer are 620 μm and 0.347 mm2.
A Cronus Sigma 1000 Series syringe pump was used for flowing electrolytes in the channel 7. The applied current to the device 1 is controlled by a Bio-Logic SP-300 potentiostat. The images of the bubbles generation and flow is captured using a Photron FASTCAM Mini UX100 camera at the 4000 fps and 1/10000 s shutter speed. Two test tubes are filled with liquid electrolyte. These test tubes are held inversely in a larger container of the liquid electrolyte. The generated hydrogen and oxygen are collected in these test tubes. The diluted gas with air is injected to the SRI 8610C gas chromatogram with a thermal conductive detector. The current is applied to the device for 15 minutes in each experiment. The experiments are repeated three times at each current density and Re.
The Re is calculated using the following equation:
where ρ, V, D, and μ are the density of the electrolyte, average velocity at the inlet of the device, hydraulic diameter of the inlet, and viscosity of the electrolyte, respectively. The density and viscosity of 1 M sulfuric acid are 1060 kg/m3 and 0.00114 kg/m/s. The dimension of inlet is 300 μm×80 μm.
While the invention has been disclosed with reference to certain preferred embodiments, numerous modifications, alterations, and changes to the described embodiments, and equivalents thereof, are possible without departing from the sphere and scope of the invention. Accordingly, it is intended that the invention not be limited to the described embodiments and be given the broadest reasonable interpretation in accordance with the language of the appended claims. Features of one of the above described embodiments may be included in any other embodiment described herein.
The content of each reference being entirely incorporated by reference herein.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/IB2020/061035 | 11/23/2020 | WO |