MODULAR ELECTROLYZER STACK AND PROCESS TO CONVERT CARBON DIOXIDE TO GASEOUS PRODUCTS AT ELEVATED PRESSURE AND WITH HIGH CONVERSION RATE

Abstract

An electrolyzer cell, electrolyzer setup, and related methods are provided for converting gaseous carbon dioxide to gas-phase products at elevated pressures with high conversion rates via electrolysis performed by the electrolyzer cell (100″). The electrolyzer cell (100″) is a multi-stack CO.sub.2 electrolyzer cell having individual stacks (40) that each include bipolar plate assemblies that have unique gas and fluid flow architecture formed therein.

Claims

1. An electrolyzer stack (100′, 100″) to convert gaseous carbon dioxide, CO.sub.2, to at least one gas-phase product that leaves the electrolyzer stack (100′, 100″), comprising: a cathode-side end unit (26) with a gas inlet (21), a fluid inlet (23), a fluid outlet (24) and an electrical terminal; an anode-side end unit (27) with a gas outlet (22) and an electrical terminal; at least two electrolyzer cells (40) sandwiched between the cathode-side end unit (26) and the anode-side end unit (27), individual ones of the at least two electrolyzer cells (40) comprising: a cathode current collector (5; 5a, 5b, 5c, 5d); an anode current collector (10); a membrane electrode assembly comprising: an ion-exchange membrane (7) with a first side and a second side, a layer of cathode catalyst (6b) arranged on said first side in contact with the ion-exchange membrane (7), a cathode-side gas diffusion layer (6a) arranged on the layer of cathode catalyst (6b) in contact with the cathode catalyst (6b), a layer of anode catalyst (8b) arranged on said second side in contact with the ion-exchange membrane (7), an anode-side gas diffusion layer (8a) arranged on the layer of anode catalyst (8b) in contact with the anode catalyst (8b); a spacer element (9a, 9b) arranged between the cathode current collector (5; 5a, 5b, 5c, 5d) and the anode current collector (10), wherein said spacer element (9a, 9b) is configured to fix the membrane electrode assembly between the cathode current collector (5; 5a, 5b, 5c, 5d) and the anode current collector (10), wherein the cathode-side gas diffusion layer (6a) is in partial contact with the cathode current collector (5; 5a, 5b, 5c, 5d) thereby forming a cathode-side in-plane flow structure (5″) therebetween, and the anode-side gas diffusion layer (8a) is in partial contact with the anode current collector (10) thereby forming an anode-side in-plane flow structure (5′) therebetween; a sealed continuous cell gas flow path extending between a cell gas inlet (46 ) and a cell gas outlet (47) within the electrolyzer cell (40) through the cathode-side flow structure (5″); a sealed continuous cell fluid flow path extending between a cell fluid inlet (48) and a cell fluid outlet (49) within the electrolyzer cell (40) through the anode-side flow structure (5′); wherein the electrical terminal of the cathode-side end unit (26), the at least two electrolyzer cells (40) and the electrical terminal of the anode-side end unit (27) are connected electrically in series; and wherein the cell gas flow paths of the at least two electrolyzer cells (40) with gas transport channels (34, 35) extending between adjacent ones of the at least two electrolyzer cells (40) through the cathode current collector (5; 5a, 5b, 5c, 5d), the spacer element (9a, 9b) and the anode current collector (10) form a continuous gas flow path that extends from the gas inlet (21) to the gas outlet (22) to supply CO.sub.2 to ones of the cathode-side gas diffusion layers (6a) to convert the CO.sub.2 to the gas-phase product via at least one cathodic electrolysis reaction taking place in the cathode-side flow structure (5″) of the at least two electrolyzer cells (40), and to discharge the product through said gas outlet (22), and wherein the cell fluid flow paths of the at least two electrolyzer cells (40) include fluid transport channels (38, 39) extending between adjacent ones of the at least two electrolyzer cells (40) through the cathode current collector (5; 5a, 5b, 5c, 5d), the spacer element (9a, 9b) and the anode current collector (10) form a continuous fluid flow path that extends from the fluid inlet (23) to the fluid outlet (24) to supply liquid anolyte to each anode-side in-plane flow structure (5′) to complete said cathodic electrolysis reaction with at least one anodic electrolysis reaction taking place at the anode-side in-plane she flow structure (5′) of the at least two electrolyzer cells (40), and to discharge the liquid-phase anolyte and reaction product(s) forming in said anodic electrolysis reaction through said fluid outlet (24).

2. The electrolyzer stack (100′, 100″) according to claim 1, wherein: at least a part of the cell gas flow paths of the at least two electrolyzer cells (40) is connected to one another in series; or at least a part of the cell gas flow paths of the at least two electrolyzer cells (40) is connected to one another in parallel.

3. The electrolyzer stack (100′, 100″) according to claim 2, wherein the spacer element (9a, 9b) comprises an internal gas transport channel (36) passing therethrough in a first peripheral region of the spacer element (9a, 9b), said spacer element (9a, 9b) further comprising a second peripheral region located diametrically opposite to the first peripheral region, said second peripheral region being configured to act as means for selectively choose the way two adjacent cell flow paths connect to one another in the gas flow path of the electrolyzer stack (100′, 100″), said means being provided as a further internal gas transport channel (36) in the second peripheral region.

4. The electrolyzer stack (100′, 100″) according to claim 1, wherein an assemblage assisting recess (52) is formed in a peripheral edge of the cathode-side end unit (26), the anode-side end unit (27), the cathode current collector (5; 5a, 5b, 5c, 5d), the spacer element (9a, 9b) and the anode current collector (10) of the at least two electrolyzer cells (40) of the electrolyzer stack (100′, 100″) to assist assembling/reassembling of the stack (100′, 100″).

5. The electrolyzer stack (100′, 100″) according to claim 1, wherein a cathode-side pressure chamber (31) is formed in the cathode-side end unit (26), and an anode-side pressure chamber (32) is formed in the anode-side end unit (27), wherein said continuous gas flow path is directed through the cathode-side pressure chamber (31) and the anode-side pressure chamber (32) to provide adaptive pressure control on the electrolyzer cells (40) and thus to provide uniform pressure distribution throughout said electrolyzer cells (40).

6. The electrolyzer stack (100′, 100″) according to claim 1, wherein the cathode current collector (5; 5a, 5b, 5c, 5d) of individual ones of the at least two electrolyzer cells (40) is formed as a second component (40b) of a two-component bipolar plate assembly (40′), and the anode current collector (10) of individual ones of the at least two electrolyzer cells (40) is formed as a first component (40a) of the two-component bipolar plate assembly (40′).

7. The electrolyzer stack (100′, 100″) according to claim 6, wherein the second component (40b) of the two-component bipolar plate assembly (40′) comprises a system of cathode-side in-plane flow-channels (5″) in a surface thereof facing the ion-exchange membrane (7).

8. The electrolyzer stack (100′, 100″) according to claim 6, wherein the first component (40a) of the two-component bipolar plate assembly (40′) comprises a system of anode-side in-plane flow-channels (5′) in a surface thereof facing the ion-exchange membrane (7).

9. The electrolyzer stack (100′, 100″) according to claim 6, wherein said first and second components (40a, 40b) of the two-component bipolar plate assembly (40′) further comprise ports (41, 42, 43, 44, 46, 47, 48, 49) and respective cavities (33a, 33b, 33c, 33d) fully surrounding said ports for fluid/gas communication between opposite side surfaces of said first and second components (40a, 40b).

10. The electrolyzer stack (100′, 100″) according to claim 9, wherein the cavities (33a, 33b, 33c, 33d) are sealed separately when the stack (100, 100 ″) is assembled.

11. The electrolyzer stack (100′, 100″) according to claim 1, wherein the anode-side gas diffusion layer (8a) of individual ones of the at least two electrolyzer cells(40) is chosen from a group consisting of Ti-frits in the form of pressed Ti powder of different average particle size, Ni-frits in the form of pressed Ni powder of different average particle size, Ti-mesh and Ni-mesh.

12. The electrolyzer stack according to claim 1, wherein the cathode catalyst (6b) is chosen from a group consisting of Ag/C catalyst and Cu/C catalysts.

13. The electrolyzer stack according to claim 1, wherein the anode catalyst (8b) is chosen from a group consisting of IrO.sub.x, RuO.sub.x, NiO.sub.x and TiO.sub.x.

14. The electrolyzer stack (100′, 100″) according to claim 1, wherein the at least two electrolyzer cells (40) include at most ten electrolyzer cells (40).

15. An electrolyzer setup (200) to convert gaseous carbon dioxide, CO.sub.2, to at least one gas-phase product, the setup (200) comprising: an electrolyzer stack (100′, 100″) according to claim 1; a source (201) of gaseous CO.sub.2; a source of liquid anolyte (213); an external power source (220) with a first pole of a first electrical charge and a second pole of a second electrical charge, the second electrical charge being opposite in sign compared to the first electrical charge; the first pole electrically coupled to the electrical terminal of the cathode-side end unit (26) of the electrolyzer stack (100′, 100″) and the second pole electrically coupled to the electrical terminal of the anode-side end unit (27) of the electrolyzer stack (100′, 100″); a cathode-side circulation assembly configured to circulate the gaseous CO.sub.2 from said source (201) of gaseous CO.sub.2 through the gas flow path of the electrolyzer stack (100′, 100″) to at least one product receptacle; and an anode-side circulation assembly configured to circulate the liquid anolyte (213) from said source of liquid anolyte (213) and through the fluid flow path of the electrolyzer stack (100′, 100″).

16. The electrolyzer setup (200) according to claim 15, wherein the cathode-side circulation assembly further comprises a humidifier (203) arranged upstream of the electrolyzer stack and configured to humidify the CO.sub.2 before being supplied into the electrolyzer stack (100′, 100″).

17. The electrolyzer setup (200 ) according to claim 15, wherein the cathode-side circulation assembly further comprises a back-pressure regulator (209) arranged downstream of the electrolyzer stack (100′, 100″) and configured to increase a pressure difference prevailing in the electrolyzer stack (100′, 100″).

18. The electrolyzer setup (200) according to claim 15, wherein the cathode-side circulation assembly further comprises a water separator (208) arranged downstream of the electrolyzer stack (100′, 100″) and upstream of a back-pressure regulator (209) and configured to remove moisture from the gaseous product(s).

19. The electrolyzer setup (200) according to claim 15, wherein the anode-side circulation assembly also comprises a liquid anolyte refreshing unit (211) configured to refresh the anolyte (213) and/or to separate the reaction product(s) forming in the anodic electrolysis reaction(s) from the anolyte (213).

20. The electrolyzer setup (200) according to claim 19, wherein the anolyte refresher unit (211) is in thermal coupling with a tempering means (212) to adjust the temperature of the anolyte (213).

21. The electrolyzer setup (200) according to claim 15, wherein the anolyte is an aqueous KOH solution.

22. A method to convert gaseous carbon dioxide, CO.sub.2, to at least one gas-phase product, the method comprising: circulating gaseous CO.sub.2 through an electrolyzer stack (100′, 100″) according to claim 1; simultaneously with the circulating gaseous CO.sub.2, circulating liquid anolyte (213) through the electrolyzer stack (100′, 100″); and while keeping the CO.sub.2 and the anolyte in circulation, performing cathodic electrolysis reactions and anodic electrolysis reactions in the electrolyzer stack (100′, 100″) to convert the gaseous CO.sub.2, in continuous flow, to the at least one gas-phase product; separating the at least one gas-phase product from the gaseous CO.sub.2; and discharging the at least one gas-phase product.

23. The method according to claim 22, further comprising using Ag/C cathode catalyst to produce a mixture of hydrogen and carbon monoxide as the gas-phase product.

24. The method according to claim 22, further comprising using Cu/C cathode catalyst produce ethylene as the gas-phase product.

25. The method according to claim 22, further comprising refreshing the liquid anolyte (213).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In what follows, the invention is described in detail with reference to the accompanying drawings, wherein

[0038] FIG. 1 illustrates simplified operation of a carbon dioxide electrolyzer setup according to the invention fed with (humidified) CO.sub.2 gas on the cathode side and with tempered anolyte on the anode side of the electrolyzer cell/stack used therein;

[0039] FIG. 2A is a schematic cross-sectional representation of a single-layered electrolyzer cell usable in the carbon dioxide electrolyzer setup shown in FIG. 1;

[0040] FIG. 2B is an expanded view of a part of the cell exemplified in FIG. 2A;

[0041] FIGS. 3A and 3B are complete upper and lower, respectively, perspective views of a specific exemplary embodiment of an electrolyzer stack according to the invention with three cells used to convert carbon dioxide gas to various gas-phase products;

[0042] FIG. 4 is a partially exploded view of a multi-cell electrolyzer stack according to the invention comprising n cells with one electrolyzer cell exploded;

[0043] FIG. 5 is a bottom view of a preferred two-component bipolar plate assembly used as the first (anodic) component of an intermediate electrolyzer cell (cell i+1) of the stack, as well as the second (cathodic) part of an adjacent intermediate electrolyzer cell (cell i) of the stack (here, 0<i<n−1, i, n are integer numbers);

[0044] FIG. 5A is a cross-sectional view of the bipolar plate assembly illustrated in FIG. 5 along the A-A section;

[0045] FIG. 5B is a cross-sectional view of the bipolar plate assembly illustrated in FIG. 5 along the B-B section;

[0046] FIG. 6 is a cross-sectional view of a 3-cell stack along the A-A section shown in FIG. 3A assembled to accomplish a parallel flow configuration in terms of CO.sub.2 supply of the stack; here, the system of flow-channels and cavities shown in grey represents the way of gas flow within the stack from the CO.sub.2 inlet to the CO.sub.2 and product outlet;

[0047] FIG. 7 is a cross-sectional view of the 3-cell stack along the A-A section shown in FIG. 3A assembled to accomplish a serial configuration in terms of CO.sub.2 supply of the stack; here, the system of flow-channels and cavities shown in grey represents the way of gas flow within the stack from the CO.sub.2 inlet to the CO.sub.2 and product outlet;

[0048] FIG. 8 is a cross-sectional view of the 3-cell stack along the B-B section shown in FIG. 3A in the serial/parallel configuration; here, the system of flow-channels and cavities shown in grey represents the way of fluid (i.e. anolyte) flow within the stack from the anolyte inlet to the anolyte and anodic product (in particular O.sub.2 when water is used as anolyte) outlet;

[0049] FIG. 9 illustrates various flow patterns formed in the surface of the cathode current collector used in the electrolyzer stack according to the present invention; here FIGS. 9(a) to (c) show some exemplary designs with CO.sub.2 fed into the cell at the centre and CO.sub.2 collection from the cell along an outer peripheral ring, while Figure (d) shows a further exemplary design with CO.sub.2 fed into the cell on the perimeter of the cathode current collector and CO.sub.2 collection from the cell also on the perimeter of the cathode current collector, but at a position located opposite relative to the point where CO.sub.2 is introduced, after passing over a double spiral pattern;

[0050] FIG. 10A illustrates a possible preferred embodiment of the anode-side spacer element used to accomplish a serial gas flow configuration between two adjacent cells/bipolar plate assemblies in a multi-cell electrolyzer stack upon assemblage;

[0051] FIG. 10B illustrates a possible preferred embodiment of the anode-side spacer element used to accomplish a parallel gas flow configuration between two adjacent cells/bipolar. plate assemblies in a multi-cell electrolyzer stack upon assemblage;

[0052] FIGS. 11A and 11B show a possible preferred embodiment of the anode current collector, that is, the anodic part of the bipolar plate assembly in FIG. 5, in top and bottom views, respectively, formed with a flow pattern in one of its side surfaces, highlighting the cavities formed for O-ring sealings;

[0053] FIGS. 12A and 12B are exploded views of a single cell in a multilayered electrolyzer stack assembled with serial or parallel gas flow configurations, respectively;

[0054] FIG. 13 illustrates the effects of the increase in the number of individual electrolyzer cells applied in the electrolyzer stack according to the present invention assembled in either a serial or a parallel gas flow configuration; in particular, in plot (a), the CO.sub.2 conversions during electrolysis at ΔU=−2.75 V/cell achievable with a 1-cell and a 3-cell serial connected electrolyzer at different CO.sub.2 feed rates are plotted, and in plot (b), the CO.sub.2 conversion during electrolysis at different cell voltages achievable with an electrolyzer stack consisting of one cell or three cells, connected in parallel (with identical cell normalized gas feed), are shown;

[0055] FIG. 14 shows current density versus operational cell-voltage of a 3-cell CO.sub.2 electrolyzer stack according to the invention used for syngas (H.sub.2/CO mixture on Ag catalyst) or hydrocarbon (CH.sub.4 and C.sub.2 H.sub.4 on Cu catalyst) formation, recorded by linear sweep voltammetry (LSV) at v=10 mV s.sup.−1 sweep rate with different catalyst containing cathode gas diffusion electrodes (GDEs);

[0056] FIG. 15 is a chronoamperometric curve taken at ΔU=−3 V/cell for a 3-cell CO.sub.2 electrolyzer stack according to the present invention, using a 1 mg cm.sup.−2 Ag containing cathode GDE, immobilized on Sigracet39BC carbon paper by spray coating;

[0057] FIG. 16 presents gas chromatograms recorded during a chronoamperometric measurement at ΔU=−2.75 V/cell performed with a a 3-cell CO.sub.2 electrolyzer stack according to the present invention, using Ag catalyst [plot (a)] or Cu catalysts [plot (b)];

[0058] FIG. 17 shows partial current densities for CO and H.sub.2 formation (ordinates to the left), as well as the ratio of the partial current densities (ordinates to the right) at different stack voltages (obtained by chronoamperometric and gas chromatography measurements);

[0059] FIG. 18 partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the Ag catalyst amount in the cathode GDE;

[0060] FIG. 19 shows partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the applied cathode spacing;

[0061] FIG. 20 presents partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the depth of the flow-pattern applied in the cathodic side of the electrolyzer stack according to the invention;

[0062] FIG. 21 illustrates partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of carbon-dioxide flow rate (normalized with the surface area) in the cathode compartment of the electrolyzer stack according to the invention;

[0063] FIG. 22 shows partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the anolyte (1M KOH) temperature (at ˜9 cm.sup.3 cm.sup.−2 min.sup.−1 feed rate) taking place in the electrolyzer stack according to the invention;

[0064] FIG. 23 presents LSV curves recorded at v=10 mV s.sup.−1 sweep rate under various differential CO.sub.2 pressures during electrolysis performed in the electrolyzer stack according to the invention; and

[0065] FIG. 24 shows current densities at different stack voltages (plot A) and the ratio of the partial current densities (plot B) during electrolysis at ΔU=−2.75 V, both as a function of the differential CO.sub.2 pressure.

DESCRIPTION OF POSSIBLE ELEMENTS

[0066] FIG. 1 illustrates an exemplary embodiment of a CO.sub.2 electrolyzer setup 200 comprising a CO.sub.2 electrolyzer (electrochemical) stack 100 used to generate gaseous products at elevated pressures with high conversion rates via the electrolysis of gaseous CO.sub.2 fed into the stack 100 which comprises a cathode 101 on a cathodic side, an anode 103 on an anodic side and a separator 102 to separate said cathode 101 and anode 102 from one another; here, the separator 102 is preferably a PEM element (e.g., an anion exchange membrane or a cation exchange membrane or a bipolar membrane). Said stack 100 is equipped with at least one gas inlet 101a and at least one gas outlet 101b, both being in gas connection with the cathodic side of the stack 100. Said stack 100 is also equipped with at least one fluid inlet 103a and at least one fluid outlet 103b, both being in fluid connection with the anodic side of the stack 100. The setup 200 further comprises a source 201 of gaseous CO.sub.2, a humidifier 203 to humidify the gaseous CO.sub.2, a power supply 220 to energize the electrochemical stack 100, an anolyte refresher unit 211 to regenerate an anolyte 213 used in the anodic side of the stack 100, a water separator 208 to remove moisture from the gaseous product(s) produced via the elecrolysis of gaseous CO.sub.2 in the cathodic side of the stack 100, a back pressure regulator 209 to pressurize the stack 100 to maintain an elevated pressure (up to 30 bars, preferably up to 20 bars) within the stack 100, as well as a gaseous product outlet 216 that opens into a gas-phase product receptacle (not illustrated). As the CO.sub.2 source 201, either a source of pure gaseous CO.sub.2 or a source that supplies CO.sub.2 in the form of a gas mixture, can be used. Optionally, the setup 200 further comprises any of a mass flow controller 202 to accurately control the mass flow of the gaseous CO.sub.2 fed into the cathodic side of the stack 100 and appropriate pressure gauges 210, 210′ to characterize the pressure prevailing within the stack 100. The CO.sub.2 source 201 is connected to the gas inlet 101a of the stack 100 via an appropriate pipe 204, while the product outlet 216 is connected to the gas outlet 101b of the stack 100 via a further pipe 207. As a result, a continuous flow-path forms from said CO.sub.2 source 201 to the product outlet 216 through the cathodic side of the stack 100. The mass flow controller 202 is preferably inserted into the pipe 204 downstream of the CO.sub.2 source 201. The humidifier 203 is preferably inserted into the pipe 204 downstream of the mass flow controller 202, to humidify the gaseous CO.sub.2 before its entry into the stack 100. The humidifier 203 is preferably a temperature-controlled bubbling type humidifier, however, any other kind of humidifier can also be applied here. Optionally, the pressure gauge 210 is also inserted into the pipe 204 to continuously monitor the inlet pressure in the stack 100. The water separator 208 is inserted into the pipe 207 downstream of the stack 100. The back pressure regulator 209 is inserted into the pipe 207 downstream of said water separator 208. As the water separator 208 and the back pressure regulator 209 any kind of water separator and pressure regulator can be used, as is clear for a skilled person in the art. Optionally, the further pressure gauge 210′ is inserted into the pipe 207 between the stack 100 and the back pressure regulator 209 to continuously monitor the outlet pressure in the stack 100. Thus, by means of the pressure gauges 210, 210′, the pressure drop through the stack 100 can also be determined.

[0067] The anodic side of the stack 100 is in fluid connection through its fluid outlet 103b and a pipe 205 with an inlet port 211a of the anolyte refresher unit 211. Furthermore, the anodic side of the stack 100 is in fluid connection through its fluid inlet 103a and a pipe 206 with an outlet port 211b of the anolyte refresher unit 211. Thus, a closed continuous flow-path forms on the anodic side of the stack 100 between said anodic side and the anolyte refresher unit 211. Through this closed flow-path, an anolyte 213 is circulated by means of a pump 215 inserted preferably into the pipe 206 between the anodic side, through an appropriate system of fluidic channels formed in the anode, and the refresher unit 211 to refresh spoilt anolyte (if needed) taking place in electrochemical reaction(s) at the anodic side in the stack 100. Furthermore, to provide the possibility of venting in said anolyte refresher unit 211, said unit is also equipped with venting means 214 through which surplus gas accumulating in the refresher unit 211 separated from spoilt anolyte 213 during the process of refreshment of the anolyte 213 can leave the unit. For the optimal operation of the CO.sub.2 electrolyzer setup 200, and in turn the stack 100 as well, the anolyte refresher unit 211 is in thermal coupling with appropriate tempering means 212 to adjust the temperature of the anolyte 213, that is to cool/heat it. To this end, as is clear for a skilled person in the art, any kind of tempering means, that is, cooler/heater means can be used.

[0068] As far as the electric power supply of the stack 100 is concerned, a negative pole of said power supply 220 is electrically connected with the cathodic side of the stack 100, in particular a cathode-side contact plate, while a positive pole of said power supply 220 is electrically connected with the anodic side of the stack 100, in particular an anode-side contact plate (to be discussed later in detail). Said power supply 220 can be either the grid itself or any local source of electricity, i.e. a solar, wind, nuclear one. A battery, either a disposable or a secondary one, can be equally used as the power supply 220.

[0069] In operation, the carbon dioxide (either pure, or a gas mixture) is first humidified at a controlled temperature (which is preferentially in the range of about 20° C. to about 70° C.), and then fed to the cathodic side of the stack 100. Here, there is no solution feed to the cathode. When feeding only humidified CO.sub.2 gas to the cathodic side, the reactant concentration remains very high on the catalyst, and therefore high reaction rates (currents) can be achieved. Furthermore, because the lack of solution feed, no reactant is washed out unreacted with this stream. As the type of reactant has an important and complex effect on stack performance, this modification regarding the type of feed represents a significant difference in comparison with most prior art solutions. In the presented CO.sub.2 electrolyzer setup 200, only gas phase products form in the electrolysis reactions that take place in the stack 100. Depending on the catalysts used in the stack 100 and the applied CO.sub.2 electrolysis reactions (see Table 1) various products are obtained; as examples (i) syngas (CO/H.sub.2 mixture with controlled composition) and (ii) ethylene are mentioned here. The gaseous products forming in the cathodic part, that is, within the system of flow-channels fabricated in cathode-side constructional elements (discussed later), leave the stack 100 and then are introduced into the water separator 208 to remove moisture. The anolyte 213 (employed as aqueous solution, the type of which depends on the type of separator 102 used, i.e. the applied ion-exchange membrane) is directly and continuously fed into the anodic side of the stack 100 with the pump 215. Said anolyte 213 then flows through the stack 100 in a system of flow-channels fabricated in anode-side constructional elements and collects gaseous oxygen that forms in the electrolysis reaction of CO.sub.2 along its path.

[0070] When the stream of anolyte 213 leaves the stack 100, and before being recirculated into said stack 100, the oxygen content in said anolyte 213 gets released within the anolyte refresher unit 211 and then is vented out through said venting means 214. Notably, other value-added anode processes (other than water oxidation, e.g. chlorine formation or alcohol oxidation) can be coupled to CO.sub.2 conversion, as is clear for a skilled person in the art; the architecture of said setup 200/stack 100 is not confined to water oxidation at all. Furthermore, during operation of the setup 200, the pressure in the stack 100 is continuously controlled by the back pressure regulator 209. Thus, contrary to most prior art solutions, the electrolyzer stack 100 actually works under continuous differential pressure.

[0071] FIG. 2A is the schematic cross-sectional view of a single exemplary PEM electrolyzer cell that can be used in the CO.sub.2 electrolyzer stack 100/setup 200 shown in FIG. 1; FIG. 2B is an expanded view of a part of the cell taken in the vicinity of the b-b line shown in FIG. 2A. Said cell comprises a PEM, in particular an ion-exchange membrane 7, 102, held in place by (i.e. cathode- and anode-side) spacer elements 9(a,b) arranged at opposite sides of said membrane 7 along its peripheral edge portion. The membrane 7 functions as a separator element, it separates the cathode 101 and the anode 103 (i.e. the cathodic and anodic sides) of the cell from one another. At the cathodic side, there is a layer of (cathode) catalyst 6b arranged adjacent to and in direct contact with the membrane 7. On the layer of the catalyst 6b, on a surface thereof facing away the membrane 7, a gas diffusion layer 6a is arranged in direct contact with said layer of catalyst 6b. On this gas diffusion layer 6a, a plate of a cathode current collector 5 is arranged in direct contact with said gas diffusion layer 6a.

[0072] Here, the membrane 7 is an anion exchange membrane, available under the tradenames of e.g. Fumasep, Selemion and Sustanion, just to mention a couple of examples only, which allows, in operation, the migration of hydroxide ions (OH.sup.− ions; charges, and thus current) between the cathodic and anodic sides of the cell through its bulk, while water (H.sub.2O) diffusing through it from the anodic to the cathodic side takes part in the electrolytic reduction of CO.sub.2 at the cathodic side. As in this case no electrons are transported through the membrane 7, said membrane 7 actually acts as a layer of electrical insulation between the cathodic and anodic sides of the cell. As is clear for a skilled person in the art, depending on the electrolytic reaction to be performed at the cathodic side, cation exchange membranes, available under the tradenames of e.g. Nafion and Aquivion, or further bipolar membranes (e.g. Fumasep FBM) can equally be employed as the membrane 7.

[0073] The cathode current collector 5, on the one hand, acts as a current distributing lement, that is, it uniformly distributes the electric current received from an external power supply through a cathode-side contact plate (discussed below) over the cathode-side gas diffusion layer 6a and, on the other hand, provides appropriate space for the compression of said cathode-side gas diffusion layer 6a. The cathode current collector 5 comprises a system of in-plane flow-channels 5″ of height M formed on/in a surface of the cathode current collector 5 that faces towards the membrane 7; said system of flow-channels 5″ corresponds to various geometrical patterns (see e.g. FIG. 9). The patterned formation of the flow-channels 5″ allows a uniform distribution of the gaseous CO.sub.2 over the cathode-side gas diffusion layer 6a. The cathode current collector 5 is also provided with, in the form of throughout openings, an inlet for feeding gaseous CO.sub.2 to the gas diffusion layer 6a and an outlet for discharging the gaseous product that forms at the cathodic side of the cell in the electrolysis reaction (reduction) of CO.sub.2.

[0074] The cathode-side gas diffusion layer 6a allows, in operation, a CO.sub.2 transport to the layer of cathode catalyst 6b in contact with the membrane 7 where reduction reaction of the gaseous CO.sub.2 takes place and thus the desired product forms. The gas diffusion layer 6a also allows the transport of said gaseous product (in the form of a mixture also comprising the amount of non-converted CO.sub.2) along the cathodic flow-channel structure towards a CO.sub.2 and product outlet of the cell. To provide effective transport properties, as the cathode-side gas diffusion layer 6a any of a carbon cloth, carbon felt and carbon film can be used, preferably modified with a microporous layer, as is known by a skilled person in the art. As the cathode catalyst 6b, a plurality of catalysts can be used, the cathode catalysts applied in this case are preferably Ag/C and Cu/C catalysts. The gas diffusion layer 6a and the layer of cathode catalyst 6b have a total thickness H, as is shown in FIG. 2B, that represents cathode compartment spacing.

[0075] In turn, at the anodic side, there is a layer of anode catalyst 8b arranged adjacent to and in direct contact with the membrane 7; here, IrO.sub.x, RuO.sub.x, NiO.sub.x, and TiO.sub.x are highly preferred anode catalysts. On the layer of the anode catalyst 8b, on a surface thereof facing away the membrane 7, an anode-side gas diffusion layer 8a is arranged in direct contact with said layer of anode catalyst 8b. Said anode-side gas diffusion layer 8a is formed of a layer of titan-frit (Ti-frit) in the form of pressed Ti powder of different average particle size (in the range of preferably 50-200 μm) or a layer nickel-frit (Ni-frit) in the form of pressed Ni powder of different average particle size (in the range of preferably 50-200 μm), titan-mesh (Ti-mesh) or nickel-mesh (Ni-mesh), both having a wire thickness and pore size preferably in the range of 50-200 μm, just to mention a few examples. On the anode-side gas diffusion layer 8a, a plate of an anode current collector 10 is arranged in direct contact with said gas diffusion layer 8a. The anode current collector 10 also comprises a system of flow-channels 5′ formed in a surface of the anode current collector 10 that faces towards the membrane 7.

[0076] The anode current collector 10, on the one hand, acts as a current distributing element, that is, it uniformly distributes the electric current received from the external power supply through an anode-side contact plate (discussed below) over the anode-side gas diffusion layer 8a and, on the other hand, provides appropriate space for the compression of the anode-side gas diffusion layer 8a. The anode current collector 10 is also provided with, in the form of through openings, an inlet for feeding liquid anolyte to the anode-side gas diffusion layer 8a and an outlet for discharging the mixture of liquid anolyte and anodic products (e.g. gaseous O.sub.2 if the anolyte also contains water) appearing at the anodic side of the cell in the electrolysis reactions (oxidation) of the anolyte taking place at the anodic side.

[0077] As is clear for a skilled person in the art, the cathode-side gas diffusion layer 6a, the layer of cathode catalyst 6b, the membrane 7, the layer of anode catalyst 8b and the anode-side gas diffusion layer 8a can be combined into a single unit, i.e. a membrane electrode assembly, and applied in the form of said assembly to construct a modular electrolyzer cell by arranging such a membrane electrode assembly between the cathode current collector 5 and the anode current collector 10 both in electrical contact and in gaseous/fluid communication therewith and positioning said assembly properly by the anode-side spacer elements 9a, 9b. It should be here also noted that the electrolyzer cell obtained in this way and shown in FIG. 2 is essentially a zero-gap electrolyzer cell and, as discussed below, can also be used to construct multi-cell CO.sub.2 electrolyzer stacks 100″ of modular structure.

[0078] FIGS. 3 and 4 illustrate exemplary multi-cell electrolyzer stacks 100′, 100″ with more than one electrolyzer cell modules. In particular, FIGS. 3A and 3B are the upper and lower, respectively, perspective views of an electrolyzer stack 100′ comprising three electrolyzer cells used to convert gaseous CO.sub.2 to gaseous products at elevated pressures and with high conversion rates via electrolysis. FIG. 4 is a partially exploded view of a multi-cell electrolyzer stack 100″ according to the invention which comprises n cells 40 (n is a positive integer) with one electrolyzer cell exploded in the series of cells 40. According to practical considerations, however, one chooses the number n to range from at least one to even ten or more; in particular, the number n of the applied cells is preferably between two and seven, more preferably between three and six, and most preferably it is three, or four, or five, or six in one electrolyzer stack 100″.

[0079] As can be seen in FIGS. 3A, 3B and 4, the electrolyzer stacks 100′, 100″ are of modular construction, the components used to construct the stacks 100′, 100″ are provided in the form of plate-like elements of different function. The plate-like components may be of arbitrary planar shape; in the exemplary embodiments illustrated in FIGS. 3A, 3B and 4, the components are essentially circular in shape. Furthermore, to assist fast assembling and/or reassembling of said components into the stacks 100′, 100″, each of the plate-like components is provided with an assemblage assisting recess 52 formed in the peripheral edge thereof. The assemblage assisting recesses 52 thus clearly show how to combine the components into a stack properly; at the correct arrangement/orientation of the components, said recesses 52 are aligned.

[0080] Upon assembling said components into a stack, the obtained stack contains the individual electrolyzer cells side by side along a longitudinal direction. Here, and from now on, the term “longitudinal” refers to a direction that is essentially perpendicular to the surface planes of said plate-like components. Thus, as is shown in FIGS. 3A, 3B and 4, the plate-like components are provided with a plurality of through holes along said longitudinal direction. A part of said holes serves as bore holes 1a to receive screws 1 with shrink tubes and pads used to assemble said components into the stacks 100′, 100″ and then to connect said components in a sealed manner by means of screw-nuts 14 with pads screwed onto the screws 1 inserted into the respective bore holes 1a. The remaining part of the holes formed in said plate-like components, configured to be properly aligned with one another and sealed by means of specific channel sealing means (detailed below) that can be arranged around each of the holes and between the plate-like components, serves to form a longitudinal flow-through portion of the cathodic and anodic side transport channel structures within the stacks 100′, 100″. In particular, at the cathodic side, one of said holes serves as a gas inlet 21 to introduce gaseous CO.sub.2 into the electrolyzer cells 40 assembled either in serial or parallel (or in mixed) configuration in terms of CO.sub.2 supply and transport within the stack, while another two of said holes serve (i) as a fluid inlet 23 to introduce a liquid anolyte into the electrolyzer cells 40 assembled in serial/parallel configuration and (ii) as a fluid outlet 24 to discharge spoilt anolyte with gaseous anodic products (e.g. O.sub.2) that form in the individual cells 40 in the anode-side electrolysis reaction(s). In turn, at the anodic side, one of said holes serves as a gas outlet 22 to discharge non-reacted CO.sub.2 fed in in surplus with gaseous cathodic products that form in the cells 40 in the cathode-side electrolysis of CO.sub.2.

[0081] Referring now to FIG. 4, the multi-cell CO.sub.2 electrolyzer stack 100″ according to the invention is used to decompose gaseous CO.sub.2 by electrolysis and thus, depending on the applied catalysts and the anolyte, to generate various gaseous products. To this end, the stack 100″ comprises a certain number n of electrolyzer cells 40 arranged adjacent to and in sealed fluid/gaseous communication with each other through the longitudinal portion of the cathodic and anodic side transport channel structures. Furthermore, said electrolyzer cells 40 are coupled electrically with one another and the electrical terminals of the stack 100″, i.e. with the cathode-side and anode-side contact plates 4, 11 in series. Thus, the stack 100″ contains a series of electrolyzer cells 40 consisting of interconnected intermediate cells sandwiched between a cathode-side end unit 26 and an anode-side end unit 27 arranged at opposite ends of said series along the longitudinal direction.

[0082] The cathode-side end unit 26 closes the series of electrolyzer cells 40 at the cathodic side of the stack 100″. An inner surface of the cathode-side end unit 26 is in direct contact with the first cell 40 of said series, while an outer surface of the cathode-side end unit 26 is, in practice, exposed to the environment. The cathode-side end unit 26 is itself of a modular structure; it comprises a cathode-side contact plate 4 with the inner surface concerned, a cathode-side insulation 3 arranged on said cathode-side contact plate 4 and a cathode-side endplate 2 with said outer surface arranged on the cathode-side insulation 3. The cathode-side endplate 2 is provided with openings that are in gaseous/fluid communication with the cathodic and/or anodic transport channel structures, respectively, of the stack 100″ through respective openings formed in the insulation 3 and the contact plate 4 in proper alignment with the openings concerned, that is, the gas inlet 21 for CO.sub.2 supply, the fluid inlet 23 for anolyte supply and the fluid outlet 24 for spoilt anolyte (and anodic product) discharge. In the assembled state of the stack 100″, the openings formed in the cathode-side end unit 26 in alignment with one another form continuous longitudinal sealed flow-channels, each of which opens into the respective opening of the first electrolyzer cell 40. Here, sealing is achieved by appropriately sized sealing elements, preferably in the form of O-rings 15, 16, 17 made of a corrosion resistant plastic material (e.g. Viton®), arranged between the endplate 2 and the insulation 3, the insulation 3 and the contact plate 4, as well as the contact plate 4 and said first cell around the respective openings. The cathode-side endplate 2 serves as a mechanical strengthening element and to enhance pressure-tightness of the stack 100″ by means of the through screws 1. The cathode-side insulation 3 serves as an electrical insulation between the endplate 2 and the cathode-side contact plate 4. The cathode-side insulation 3 also accommodates a cathode-side pressure chamber that inhibits possible displacements of the inner components of the stack 100″ towards the cathode-side endplate 2 when the stack 100″ becomes pressurized upon starting its operation. Said pressure chamber is formed as a hollow cavity in the bulk of the cathode-side insulation 3 and extends over a given portion of the cathode-side endplate 2 when the stack 100″ is assembled. In such a case, the cathode-side pressure chamber is sealed by an O-ring 15 arranged in a circular groove around said cavity in the cathode-side insulation 3 between the insulation 3 and the endplate 2. Furthermore, the cathode-side contact plate 4 serves as an electrical connection to an external electrical power source and simultaneously as a current distributing element that uniformly distributes the electric current received from said power source through the inner surface of the cathode-side end unit 26 over the outermost surface of the very first cell in the series of intermediate cells 40. The cathode-side contact plate 4 also helps with the feed-in of the gaseous CO.sub.2 into the first electrolyzer cell 40 of the stack 100″, and with the introduction and discharge of the liquid anolyte and the spoilt anolyte into and from, respectively, the first electrolyzer cell 40 of the stack 100″.

[0083] The anode-side end unit 27 closes the series of electrolyzer cells 40 at the anodic side of the stack 100″. An inner surface of the anode-side end unit 27 is in direct contact with the last, i.e. the n-th, cell 40 of said series, while an outer surface of the anode-side end unit 27 is, in practice, exposed to the environment. The anode-side end unit 27 is itself of a modular structure; it comprises an anode-side contact plate 11 with the inner surface concerned, an anode-side insulation 12 arranged on said anode-side contact plate 11 and an anode-side endplate 13 with said outer surface arranged on the anode-side insulation 12. The anode-side endplate 13 is provided with an opening that is in gaseous communication with the cathodic transport channel structure of the stack 100″ through respective openings formed in the anode-side insulation 12 and the anode-side contact plate 11 in proper alignment with the opening at issue, i.e. the gas outlet 22 for CO.sub.2 and cathode product discharge. In the assembled state of the stack 100″, the openings formed in the anode-side end unit 27 in alignment with one another form a continuous longitudinal sealed flow-channel that opens into the corresponding opening of the last electrolyzer cell 40. Here, sealing is achieved by appropriately sized sealing elements, preferably in the form of O-rings, arranged between said last cell and the anode-side contact plate 11, the anode-side contact plate 11 and the anode-side insulation 12, as well as the anode-side insulation 12 and the anode-side endplate 13 around the openings; the O-rings concerned are similar/equivalent with the O-rings employed in the cathode-side end unit 26. Here, the anode-side contact plate 11 serves as an electrical connection to an external electrical power source and simultaneously as a current distributing element that uniformly distributes the electric current received from said power source through the inner surface of the anode-side end unit 27 over the outermost surface of the very last cell in the series of intermediate cells 40. The anode-side contact plate 11 also helps with the discharge of gaseous CO.sub.2 mixed with the electrolysis product from the last electrolyzer cell 40 of the stack 100″. The anode-side insulation 12 serves as an electrical insulation between the anode-side contact plate 11 and the anode-side endplate 13. The anode-side insulation 12 also accommodates an anode-side pressure chamber that inhibits possible displacements of the inner components of the stack 100″ towards the anode-side endplate 13 when the stack 100″ becomes pressurized upon starting its operation. Said pressure chamber is formed as a hollow cavity in the bulk of the anode-side insulation 12 and extends over a given portion of the anode-side endplate 13 when the stack 100″ is assembled. In such a case, the anode-side pressure chamber is sealed by an O-ring 15 arranged in a circular groove around said cavity in the anode-side insulation 12 between the insulation 12 and the anode-side endplate 13. Furthermore, the anode-side endplate 13 serves as a mechanical strengthening element and to enhance pressure-tightness of the stack 100″ by means of the screw-nuts 14 with pads screwed onto the screws 1 inserted through the entire structure of the stack 100″ in the bore-holes 1a from the cathode-side endplate 2. In harmony with convention, the cathode-side contact plate 4 and the anode-side contact plate 11 are in electrical connections with the negative and positive, respectively, poles of the external power source.

[0084] Referring now to FIGS. 5, 5A and 5B, which illustrate the two-component bipolar plate assembly 40′ in bottom view, in cross-sectional view taken along the A-A line and in cross-sectional view taken along the B-B line, respectively, the first component 40a of the assembly 40′ (i.e. the anode current collector 10 in a single cell) and the second component 40b of the assembly 40′ (i.e. the cathode current collector 5 (a,b,c, d) in a single cell) are provided on their opposite side surfaces with certain elements of the cathodic and anodic side transport channel structures. In particular, the first component 40a is provided with entry/exit ports for the cathode-side and anode-side systems of flow-channels within the cell 40′. Said ports are: a cell inlet gas transport channel 41 and a cell outlet gas transport channel 42 for gas supply and transport (i.e. CO.sub.2, desired product) at the cathodic side in the bipolar plate assembly 40′, as well as a cell anolyte inlet channel 48, a cell anolyte outlet channel 49, a cell anolyte transport channel 43, and a cell anolyte and anodic product transport channel 44 for fluid supply and transport (i.e. anolyte; spoilt anolyte with anodic product, e.g. gaseous O.sub.2) at the anodic side in the bipolar plate assembly 40′. The first component 40a is further provided with an in-plane system of fluid flow-channels 5′ of certain geometry on/in its side surface facing—when assembled into a stack—towards the cathode-side end unit. Said ports lead from said side surface to the opposite side surface of the first component 40b where each of said ports opens into a respective cavity which fully surrounds it, i.e. cavities 33a, 33b, 33c, 33d. Said cavities and ports provide the fluid communication with respective longitudinal fluid flow-channels 41′, 42′, 43′, 44′ formed in the second component 40b. Said second component 40b is also provided with a cell gas inlet channel 46 and a cell gas outlet channel 47 for gas supply and transport (i.e. CO.sub.2, desired product) at the cathodic side in the bipolar plate assembly 40′, as well as an in-plane system of gas flow-channels 5″ of certain geometry (see FIG. 9). Said cavities are equipped with appropriate sealing members, in particular O-rings 16, 17, 17′, 19 made of a corrosion resistant plastic material (e.g. Viton®) to seal the flow-channels when the stack is assembled and maintain pressure prevailing within the stack in operation.

[0085] The first and second components 40a, 40b of the assembly 40′ are made of the same electrically conducting compound as the other parts of the stack, which are responsible for conducting electricity, e.g. titanium, stainless steel, different alloys and composite materials. The ports and the cavities are formed by machining, in particular CNC-milling.

[0086] As is apparent from FIG. 4, after assembling the CO.sub.2 electrolyzer stack 100″ according to the invention, the cathode-side and the anode-side end units 26, 27 sandwich n pieces of practically identical intermediate electrolyzer cells 40, wherein the electrolyzer cells 40 are coupled to each other (i) in series in terms of the power (electric current) management of the stack 100″, (ii) in parallel in terms of the anolyte supply and transport within the stack 100″, and (iii) in series or parallel, or in a mixed way in terms of CO.sub.2 supply and transport within the stack 100″. Each cell 40 is constructed from the two-component bipolar membrane assemblies 40′ (see FIGS. 5A and 5B). In particular, each cell 40 comprises the first (anodic) component 40a of the i-th bipolar membrane assembly 40′, the second (cathodic) component 40b of the adjacent, i.e. (i−1)-th bipolar membrane assembly 40′ (here, 1<i<n, integer), a membrane electrode assembly discussed previously arranged between said first and second components 40a, 40b, and an anode-side spacer element 9a, 9b inserted between said first and second components 40a, 40b of the bipolar membrane assembly 40′ in the peripheral region thereof. Feature (i) is a consequence of the electric contact between subsequent cells 40 in the stack 100″. Feature (ii) is a consequence of the physical construction, i.e. the number of longitudinal channels provided in the anode-side spacer elements 9a, 9b for gas transport at the cathodic side and the orientation in which a certain spacer element 9a, 9b is actually arranged in the stack 100″. In particular, as shown in FIG. 10A, a single longitudinal channel 36 is provided in the spacer elements 9a to be used when connecting two adjacent cells so as to form a serial gas flow-channel at the cathodic side of the stack 100″; the respective configuration of the cell is illustrated in exploded view in FIG. 12A. Moreover, as shown in FIG. 10B, two longitudinal channels 36 are provided in the spacer element 9b to be used when connecting two adjacent cells so as to form gas flow-channels extending in parallel at the cathodic side of the stack 100″; here the longitudinal channels 36 are formed at diametrically opposite locations of the spacer element 9b. The respective configuration of the cell is illustrated in exploded view in FIG. 12B.

[0087] In what follows, the cathode-side gas management and the anode-side fluid management is explained in more detail for a preferred embodiment of the multi-cell electrolyzer stack 100″ comprising three individual cells 40 or bipolar plate assemblies 40′. In particular, FIG. 6 shows the 3-cell electrolyzer stack 100′ in cross-sectional view taken along the A-A line illustrated in FIG. 3A with a stack's gas flow path shown in grey; here, the stack 100′ is assembled in parallel configuration of the cell gas flow paths of the individual cells 40 in terms of CO.sub.2 supply and transport within the stack 100′. Furthermore, FIG. 7 illustrates the 3-cell electrolyzer stack 100′ in cross-sectional view taken along the A-A line shown in FIG. 3A with the stack's gas flow path shown again in grey; here, the stack 100′ is assembled in serial configuration of the cell gas flow paths of the individual cells 40 in terms of CO.sub.2 supply and transport within the stack 100′. Yet further, FIG. 8 shows the 3-cell electrolyzer stack 100′ in cross-sectional view taken along the B-B line illustrated in FIG. 3A with the stack's fluid flow path shown in grey; here, the stack 100′ is assembled in any of the serial and parallel configurations of the individual cells 40 in terms of CO.sub.2 supply and transport within the stack 100′, the cell fluid flow paths are combined to form a stack's fluid flow path in a parallel configuration in terms of anolyte supply and transport within the stack 100′.

[0088] FIG. 6 illustrates a continuous stack's gas flow path that extends from the gas inlet 21 to the gas outlet 22 through a cathode-side pressure chamber 31 formed within the cathode-side end unit, in particular in the cathode side insulation 3, then through bores formed in the cathode-side insulation 3 and the cathode-side contact plate 4 that open into a cell gas inlet 46 formed in the cathode current collector, then through said cell gas inlet 46 into grooves 45 of the flow pattern 5″ (see FIG. 9) formed in the a surface of the cathode current collector facing to the cathode-side gas-diffusion layer and thus into the first electrolyzer cell 40 arranged in the series of cells 40 applied. The stack's gas flow path then extends further as an in-plane cell gas flow path of the first cell 40 formed between the cathode-side current collector and the cathode-side gas-diffusion layer being in partial contact with each other, and leaves the first cell 40 through a cell gas outlet 47 which is in gaseous communication with a sealed cavity 33b; said cavity 33b is formed in a surface of the anode current collector. The stack's gas flow path then extends from said cavity 33b through an outlet gas transport channel 35, then through bores formed in the anode-side contact plate 11 and the anode-side insulation 12 into an anode-side pressure chamber 32 formed within the anode-side end unit, in particular in the anode-side insulation 12, then from said anode-side pressure chamber 32 to the gas outlet 22. Here, the outlet gas transport channel 35 is formed by the cell outlet gas transport channels 42′ (see FIG. 9) formed in the cathode current collector, the internal gas transport channel 36 of the anode spacer element 9b (see FIG. 10B) and the cell outlet gas transport channel 42 formed in the anode current collector (see e.g. FIG. 11A).

[0089] Furthermore, to supply CO.sub.2 into the second and the any subsequent cells 40 too, the stack's flow path extends from the cathode-side pressure chamber 31 through an inlet gas transport channel 34 into sealed cavities 33a formed in said surface of the anode current collector of the individual cells 40, wherein each of the cavities 33a is connected with the cell gas inlet 46 of the cell 40. Thus, in operation, all the cells 40 are in gaseous communication with said inlet gas transport channel 34 which means a parallel gas transport configuration of the electrolyzer stack 100′. The inlet gas transport channel 34, which is formed by a cell inlet gas transport channel 41 formed in the cathode current collector, a further internal gas transport channel 36 of the anode spacer element 9b and a cell inlet gas channel 41, ends in an inlet gas transport channel end 34a, i.e. it is a dead furrow.

[0090] FIG. 7 illustrates a continuous stack's gas flow path that extends from the gas inlet 21 to the gas outlet 22. Here, when the multi-cell electrolyzer stack 100′ is assembled, due to (i) the employment of an anode spacer member 9a that has only a single internal gas transport channel 36 (instead of two), and (ii) the fact that said anode spacer member 9a is arranged in the adjacent cells with an orientation that is rotated with just 180° about an axis perpendicular to the spacer element 9a at the centre thereof, the stack's flow path becomes a flow path of the cell flow paths connected in series as a consequence of segmentation of the inlet gas transport channel 34 and the outlet gas transport channel 35 (see FIG. 6).

[0091] FIG. 8 illustrates a continuous stack's fluid flow path that extends from the fluid inlet 23 to the fluid outlet 24 through a continuous inlet flow transport channel formed by through channel 43′ in the cathode current collector, through channel 38 in the spacer element and through channel 43 in the anode current collector of the electrolyzer cells, then through sealed cavities 33c in flow communication with cell fluid inlets 48, then through the flow patterns 5′ and through channels 49 into sealed cavities 33d, then from the cavities 33d in fluid communication with a continuous outlet flow transport channel formed by through channel 44 in the anode current collector, through channel 39 in the spacer element and through channel 44′ in the cathode current collector of the electrolyzer cells.

[0092] In what follows, the constructional components of a single electrolyzer cell 40, e.g the one illustrated in FIG. 4 as the exploded cell, constructed from two-component bipolar plate assemblies 40′ are explained in more detail with reference to FIGS. 9 to 11.

[0093] In particular, FIG. 9 shows four possible embodiments of the cathode current collector 5a, 5b, 5c, 5d (forming the second component 40b of the two-component bipolar plate assemblies used), wherein each embodiment is provided with a certain in-plane flow-channel structure or flow pattern 5″. The flow pattern 5″ is a crucial part in achieving homogeneous CO.sub.2 feed to the cathodic side of the cells and efficient product collection therefrom. Here, the CO.sub.2 feed takes place through a cell gas inlet channel 46 extending longitudinally, while product collection is performed through a cell gas outlet channel 47 extending also along the longitudinal direction. Between said inlet and outlet channels 46 and 47, the gaseous CO.sub.2 is transported and continuously involved the cathode electrolysis reaction and thus converts to the gaseous product within the grooves 45 of the continuous flow pattern 5″ which is in contact with the membrane electrode assembly (not illustrated). As it can be seen in FIG. 9, in three exemplary flow designs, namely the flow designs of FIGS. 5(a) to 5(c) corresponding to a labyrinth-type flow pattern, an offset circles-type flow pattern and a radial double spiral-type flow pattern, respectively, the gaseous CO.sub.2 is fed at the centre, i.e. the cell gas inlet channel 46 is located at the centre of the cathode current collector, and collected all along an outer ring, i.e. the cell gas outlet channel 47 is arranged in the peripheral portion of the cathode current collector. FIG. 5(d) illustrates such a further flow design, in the case of which the CO.sub.2 is fed on the perimeter of the cathode current collector and collected at e.g. a diametrically opposite location of the cathode current collector after passing through a double-spiral pattern, that is, both the cell gas inlet and outlet channels 46, 47 are located in the peripheral region of the cathode current collector. Surprisingly, it was found that unlike in fuel cells, the best performing flow patterns were always those in which CO.sub.2 was fed in the centre of the flow pattern.

[0094] It should be here noted that to use cathode current collectors 5a, 5b, 5c, 5d of different flow patterns 5″ together with the same anode current collector 10 in a multilayered stack, or putting this another way, to use the second component 40b of various flow patterns 5″ of the two-component bipolar plate 40′ with a single type first component 40a (i.e. provided with a unique flow pattern 5′) thereof, the inlet gas transport channel 41 is formed specifically. In particular, the shape of said inlet gas transport channel 41 is circular at the side of the second component 40b with the flow pattern 5″, while it has a narrow elongated shape at the opposite side of the second component 40b to cover the cell gas inlet channel 46 independent of the fact whether it is formed at the centre or in a peripheral region of the second component 40b.

[0095] FIGS. 10A and 10B show possible embodiments of the anode-side spacer elements 9a, 9b to be arranged between the cathode current collector and the anode current collector in every electrolyzer cell 40 of the multi-cell electrolyzer stack 100′, 100″ to accomplish either the serial or the parallel, respectively, cathode-side gas flow-channel configuration. The two kinds of anode-side spacer element 9a, 9b are practically identical, but the number of internal gas transport channels 36 extending in the longitudinal direction. With this unique choice of design, the anode-side spacer elements are such spacer elements that are configured to act as means for selectively choose the way two adjacent cell flow paths connect to one another in the gas flow path of the electrolyzer stack. The anode-side spacer elements 9a, 9b are made of electrical insulators, preferably plastics or Teflon. Thus, said anode-side spacer elements 9a, 9b can be simply and cheaply fabricated, even on the industrial scale and in an automated manner.

[0096] FIG. 11 presents the anode current collector 10 (which forms the first component 40a of the two-component bipolar plate assemblies) used in the CO.sub.2 electrolyzer stacks according to the invention, FIG. 11A is a top view, while FIG. 11B is a bottom view of the anode current collector 10, highlighting the cavities 33a, 33b, 33c, 33d provided for establishing a sealed gaseous/fluid communication for the gaseous/fluid management of the stack, as well as to accommodate the required sealing elements, i.e. the various O-rings.

[0097] Finally, FIGS. 12A and 12B illustrate a single cell 40 of a multi-cell electrolyzer stack assembled with serial and parallel cathode-side gas flow configurations, respectively, in exploded views. FIGS. 12A and 12B also show the advantage of the modular construction applied. In particular, by replacing the anode spacer element 9a having only a single internal gas transport channel 36 with an anode spacer element 9b comprising two internal gas transport channels 36, the flow configuration of the cell 40 concerned is simply modified from the serial one to the parallel one, and vice versa. That is, by simply disassembling the electrolyzer stack to cells and then any of the cells to components, replacing the anode spacer element(s) with anode spacer element(s) which is/are required for the desired cathode-side gas flow configuration, then reassembling each cells from the components and then the stack from the cells, a multi-cell electrolyzer stack of the desired gas flow management is obtained. Hence, the multilayered electrolyzer stack according to the invention can be simply and rapidly matched with the operational needs, and practically on the spot.

[0098] In what follows, the invention and its advantages are further discussed on the basis of experimental measurements performed specifically on CO.sub.2 electrolyzer stacks constructed with one cell or three cells, which are connected in the latter case in series/parallel.

[0099] As it was already discussed, the CO.sub.2 electrolyzer stack according to the present invention is of a construction of at least one, preferably more than one cells, i.e. its core which performs the electrolysis of CO.sub.2 is built up of individual electrolyzer cells connected electrically in series and in terms of the stack's gas management either in serial or in parallel configuration; the number of cells used to construct the stack is up to even ten or more, it ranges preferably from two to seven, more preferably from three to six, and most preferably it is three, or four, or five, or six.

EXAMPLE 1

Operation

[0100] In this example, some operational characteristics of a 3-cell stack assembled in serial configuration and then in parallel configuration (in terms of the cathode-side gas management) are compared with those of a 1 -cell stack (i.e. a single cell) in brief.

[0101] FIG. 13 illustrates the effects of the increase in the number of individual electrolyzer cells used in a possible embodiment of the stack according to the invention assembled in either a serial or a parallel gas flow configuration. In particular, in plot (a), the CO.sub.2 conversions during electrolysis at ΔU=−2.75 V/cell achieved for a 1-cell and a 3-cell serial connected stack at different CO.sub.2 feed rates are plotted. In plot (b), the CO.sub.2 conversion during electrolysis at different stack voltages achieved for a stack consisting of one cell or three cells, connected in parallel (with identical cell normalized gas feed), are shown. The series of measurements were performed feeding T=50° C. 1M KOH anolyte to the anode (at a feed rate of 1.5 dm.sup.3 min.sup.−1). As for the cathode catalyst layer, 3 mg cm.sup.−2 Ag was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode catalyst, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2. Furthermore, the CO.sub.2 flow rate was set to 8.3 cm.sup.3 cm.sup.−2 min.sup.−1 for the measurements shown in (b).

[0102] As is clear from plot (a), when three electrolyzer cells are coupled in series (compared to the 1-cell stack under the same conditions): [0103] the CO.sub.2 conversion gets improved; [0104] this effect is more pronounced at higher flow rates; and [0105] a conversion of about 40% is achieved.

[0106] As is clear from plot (b), when three electrolyzer cells are coupled in parallel (compared to the 1-cell stack under the same conditions): [0107] it is possible to increase the number of cells without changing the operational features; [0108] inside the stack, the CO.sub.2 stream is divided uniformly; and [0109] the conversion and the CO partial currents are similar in the 3-cell configuration, which is a clear proof of the scalability of the process.

[0110] FIG. 14 illustrates the current density versus the operational cell-voltage of a 3-cell CO.sub.2 electrolyzer stack according to the invention used for syngas (H.sub.2/CO mixture on Ag catalyst) or hydrocarbon (CH.sub.4 and C.sub.2H.sub.4 on Cu catalyst) formation. The curves were recorded by linear sweep voltammetry (LSV) at v=10 mV s.sup.−1 sweep rate with different catalyst containing cathode gas diffusion electrodes (GDEs). The series of measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1. As for the cathode catalyst layer, 1 mg cm.sup.−2 Ag was immobilized on Sigracet39BC carbon paper by spray coating. The Cu containing GDE was formed by electrodeposition. As for the anode catalyst layer, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. Moreover, the stack was mounted with a spacer element of 300 μm in thickness.

[0111] Electrochemistry of the cells proves the low voltage need. Due to the excellent electrical coupling among the various components of the stack, which is enhanced under pressure, the operational voltage of the stack is rather low (2.5 to 3.0 V). This translates to good energy efficiencies (40-50%). Syngas (H.sub.2/CO mixture) formation was demonstrated on Ag/C catalyst, while ethylene production was demonstrated on a Cu/C catalyst.

[0112] FIG. 15 demonstrates the stable operation of the electrolyzer stack. The shown chronoamperometric curve was taken at ΔU=−3 V/cell for a 3-cell CO.sub.2 electrolyzer stack according to the invention, using a 1 mg cm.sup.−2 Ag catalyst containing cathode GDE, immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The stack was mounted with a spacer element of 270 μm in thickness. The measurement was performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1.

[0113] FIG. 16 presents the formation of different gaseous CO.sub.2-reduction products, generated using the electrolyzer stack with different catalysts. Gas chromatograms recorded during a chronoamperometric measurement at ΔU=−2.75 V/cell performed with a 3-cell CO.sub.2 electrolyzer stack according to the present invention are shown, using a spray coated, 3 mg cm.sup.−2 Ag catalyst containing GDE [plot (a)] and Cu catalyst containing GDE, formed by electrodeposition of copper nanocubes on Sigracet39BC carbon paper [plot (b)]. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. The Ag containing GDE and the anode catalyst layer contained 15 wt % Sustanion ionomer. The stack was mounted with a spacer element of 270 μm in thickness. The measurement was performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1.

EXAMPLE 2

Voltage Dependent Product Distribution

[0114] The present example proves that the composition of the product syngas (H.sub.2/CO ratio) can be simply tuned by the voltage of the stack. The higher the stack voltage, the more H.sub.2 is generated.

[0115] FIG. 17 shows partial current densities for CO and H.sub.2 formation (ordinates to the left), as well as the ratio of the partial current densities (ordinates to the right) at different stack voltages (obtained by chronoamperometric and gas chromatography measurements), using a 3 mg cm.sup.−2 Ag containing cathode GDE, immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The stack was mounted with a spacer element of 300 μm in thickness. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1.

Example 3

Effect of Catalyst Loading

[0116] The present example proves that the rate of carbon dioxide reduction strongly depends on the immobilized cathode catalyst amount. The partial current density for CO formation reaches a maximum at an intermediate catalyst loading.

[0117] FIG. 18 shows partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO, conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the Ag catalyst amount in the cathode GDE. The Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1.

EXAMPLE 4

Effect of Cathode Spacing (GDL Compression)

[0118] The present example presents an additional benefit of the stack design according to the invention. By just changing one plastic element, the compression of the gas diffusion layer (GDL) can be varied. Notably, both the product distribution and the conversion are affected by this parameter. Importantly, if different GDLs have to be used, the stack can be quickly and easily tailored to it (unlike for the fuelcell like setups, where the gas-sealing and compression of the GDL is achieved by using a gasket of a given thickness, which has to be carefully tailored to the GDE in hand).

[0119] FIG. 19 shows partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the applied cathode spacing. As for the cathode, 1 mg cm.sup.−2 Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=1.25 cm.sup.3 cm.sup.−2 min.sup.−1.

EXAMPLE 5

Effect of flow pattern applied in the cathode current collector

[0120] The present example clearly shows that the flow pattern design (see FIG. 9) has a prominent effect on the residence time of the CO.sub.2 gas in the el ectrolyzer stack according to the invention, and hence on the stack performance. Here the effect of groove depth M (see FIG. 2B) is presented for the flow pattern of FIG. 9(a). According to this example, there is an optimal groove-depth, and thus residence time, which ensures high conversion rates.

[0121] FIG. 20 shows partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the depth M of the grooves of the flow-pattern applied in the cathodic side of the electrolyzer stack according to the invention. As for the cathode, 3 mg cm.sup.−2 Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1.

EXAMPLE 6

Effect of Carbon Dioxide Flow Rate in the Electrolyzer Stack

[0122] The present example is to prove that an increasing CO.sub.2 flow rate increases the conversion rate (current density) of the electrolyzer stack according to the invention. At the same time, the relative ratio of the converted CO.sub.2 to the feed-rate decreases (thus an optimal value for the CO.sub.2 flow rate has to be found and used).

[0123] FIG. 21 illustrates partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of carbon-dioxide flow rate (normalized with the surface area) in the cathode compartment of the electrolyzer stack according to the invention. Again, as for the cathode, 3 mg cm.sup.−2 Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1).

EXAMPLE 7

Effect of Anolyte (Stack) Temperature

[0124] The present example is to prove that high reaction rate and selectivity can be achieved at elevated temperatures, which can easily be regulated by the anolyte temperature. Importantly, the components of the electrolyzer stack are designed to withstand exposure to hot (alkaline) solutions, as exemplified in this case.

[0125] FIG. 22 shows partial current densities for H.sub.2 and CO formation (ordinates to the left) and CO.sub.2 conversion (ordinates to the right) during electrolysis at ΔU=−2.75 V as a function of the anolyte (1M KOH) temperature (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1) taking place in the electrolyzer stack according to the invention. The cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=2.5 cm.sup.3 cm.sup.−2 min.sup.−1. Again, as for the cathode, 3 mg cm.sup.−2 Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. Both catalyst layers contained 15 wt % Sustanion ionomer.

EXAMPLE 8

Effect of Pressure in the Electrolyzer Stack

[0126] The present example is to prove that at lower stack voltages the CO.sub.2 reduction, while at larger stack voltages the water reduction is the dominant cathode process. The cross-over between the two processes is shifted to larger current densities by increasing the CO.sub.2 pressure, allowing CO.sub.2 electroreduction to proceed at higher rates. The slope of the LSV curve at lower stack voltages increases gradually with the CO.sub.2 pressure. Hence, lower stack voltages are required to achieve the same current density under pressurized operation of the electrolyzer stack. This is further highlighted by tracing the LSV curves—recorded at different CO.sub.2 pressures—at given stack voltages.

[0127] FIG. 23 presents LSV curves recorded at v=10 mV s.sup.−1 sweep rate under various differential CO.sub.2 pressures ranging from 1 bar to 10 bar during electrolysis performed in the electrolyzer stack according to the invention. Again, as for the cathode, 3 mg cm.sup.−2 Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium fit. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidified (in room temperature deionized water) CO.sub.2 at a flow rate of u=12.5 cm.sup.3 cm.sup.31 2 min.sup.−1.

[0128] Furthermore, FIG. 24 shows current densities at different stack voltages (plot A) and the ratio of the partial current densities (plot B) during electrolysis at ΔU=−2.75 V, both as a function of the differential CO.sub.2 pressure prevailing in the electrolyzer stack when it continuously operates. Again, as for the cathode, 3 mg cm.sup.−2 Ag cathode catalyst layer was immobilized on Sigracet39BC carbon paper by spray coating. As for the anode, 1 mg cm.sup.−2 Ir black was immobilized on a porous titanium frit. The measurements were performed feeding T=50° C. 1M KOH anolyte continuously to the anode compartment (at a feed rate of ˜9 cm.sup.3 cm.sup.−2 min.sup.−1), while the cathode compartment was purged with humidfied (in room temperature deionized water) CO.sub.2 at a flow rate of u=12.5 cm.sup.3 cm.sup.−2 min.sup.−1.

[0129] FIG. 24 suggests that the selectivity for CO production is significantly increased by the increased CO.sub.2 pressure. Hence, this further allows controlling the syngas product composition (H.sub.2/CO ratio).

BRIEF SUMMARY

[0130] As is clear from the afore-mentioned, the present invention provides/exhibits: [0131] An electrochemical stack architecture for the efficient electrochemical conversion of carbon dioxide. [0132] Pressure handling up to 30 bar (preferably 20 bar), through the cathode-side and anode-side pressure chambers. [0133] Pressure tolerance, i.e. pressure applied to the electrolyzer stack improves the coordination of various stack components, sealing elements and electrical contacts by compensating the negative effects of imperfect matches in the dimensions of the components due to fabrication, and thus, results in enhanced stack performance. [0134] High mechanical strength components (e.g. stainless steel, titanium, metal alloys or composite material framework). [0135] Specific sealing system, including O-rings seated in recesses/grooves and a pressure chamber both at the anodic and the cathodic sides. [0136] Highly scalable stack construction, both in terms of size or physical dimensions, number of the cells and product yields due to modular construction. [0137] Multi-cell construction in serial and parallel gas feed (important for scaling up), meaning that the initial CO.sub.2 gas stream is either (i) divided within the stack and fed to all cells (parallel conversion takes place at various cells), or (ii) the whole CO.sub.2 feed go through all the cells, one after the other (serial design). [0138] The above two scenarios (i.e. serial or parallel gas management at the cathodic side) is realized with the same stack construction elements, just by different assembling which is ensured by the modular construction of the electrolyzer stack and the multifunctionality of the elements, in particular, of the anode-side spacer element, the very specific design of which allows the serial or parallel gas management in the same stack. [0139] The modularity of the stack allows to combine these two scenarios, hence to connect some of the electrolyzer cells in parallel, while others in series in the same stack. [0140] Modularity also ensures the use of different ion exchange membranes, gas diffusion layers and catalysts, without changing the overall architecture (but still maintaining pressure tolerance). [0141] High conversion rates as a consequence of [0142] direct gas feed, [0143] high pressure capability, [0144] controlled residence time (with stack geometry), [0145] specific flow patterns (central feed of CO.sub.2, radial collection of products). [0146] Novel design for connecting multiple individual cells to each other in order to facilitate gas and liquid transport within the electrolyzer stack. [0147] Wide variety of catalysts are usable in the electrolyzer, including but not limited to Sn, Pb, Ag, Cu, Au, C, Fe, Co, Ni, Zn, Ti, Mn, Mo, Cr, Nb, Pt, Ir, Rh, Ru, and different binary compositions and oxides formed thereof. [0148] Multitude of different products formed in different compositions, including but not limited to hydrogen, carbon monoxide, ethylene, methane. [0149] Capability of producing, also on the industrial scale, e.g. syngas and ethylene in CO.sub.2 electrolyzer stacks with Ag/C catalyst and Cu/C catalyst, respectively. [0150] Possibility for the optimization of the operational parameters (input flow rate, humidification, pressure, stack temperature, flow pattern and its depth, GDL compression). [0151] Tunable syngas composition is achievable simply by changing the stack voltage.

[0152] Furthermore, as is also clear to a person skilled in the art, the present inventive solutions, either considered alone or in any combination, are not limited to the exemplified embodiments, i.e. the electrolyzer stacks for converting gaseous carbon dioxide, but can also be applied in other electrochemical setups (such as e.g. N.sub.2-reduction to ammonia).

[0153] In light of the afore-mentioned, from a technological perspective, assembling multi-cell electrolyzers similar to the one illustrated in FIG. 1 instead plurality of single-cell stacks operating in parallel decreases the capital investment costs, as the stack frame and the anolyte circulation loop has to be built only once, and the inclusion of a further cell only requires an additional bipolar plate assembly, some sealing elements and an additional membrane electrode assembly.