Catalyzed cushion layer in a multi-layer electrode

Abstract

A zero-gap electrode is taught herein having a non-platinum containing catalytic coating that can be applied ex situ or in situ and that significantly reduces hydrogen overpotential. Moreover, the electrode taught herein includes a catalyzed fine mesh layer, cushion layer, and rigid backing.

Claims

1. A zero-gap electrode assembly, comprising: a fine mesh being flexible and electrically conductive, the fine mesh having a catalytic coating consisting essentially of one or more of, iridium, osmium, palladium, rhenium, rhodium, or ruthenium; a cushion layer in electrical communication with the fine mesh, the cushion layer having a catalytic coating consisting essentially of one or more of, iridium, osmium, palladium, rhenium, rhodium, or ruthenium; and a rigid backing, being electrically conductive and in electrical communication with the cushion layer.

2. The assembly of claim 1, wherein the flexible fine electrically conductive mesh comprises woven nickel wire mat having a wire diameter between 0.05 mm and 0.50 mm+/10%, and a weave density between 20 strands per inch and 60 strands per inch+/10%.

3. The assembly of claim 1, wherein the flexible fine electrically conductive mesh has a thickness between 0.05 mm and 0.50 mm+/10%, and comprises woven nickel wire mat, welded nickel wire mat, expanded nickel, louvered nickel, or a punched porous nickel plate.

4. The assembly of claim 1, wherein the cushion layer has a catalytic coating between 0.005 m and 5 m thick.

5. The assembly of claim 1, wherein the cushion layer comprises a catalyst layer thickness greater than 5 m.

6. The assembly of claim 1, wherein the cushion layer has a catalyst surface loading between 5 mmol/m.sup.2 and 120 mmol/m.sup.2.

7. The assembly of claim 1, wherein an interface between a cushion layer substrate and the catalytic coating of the cushion layer is substantially free from added roughness.

8. The assembly of claim 1, wherein the fine mesh is in electrically communicative physical contact with a cathode side of an ion-exchange membrane.

9. The assembly of claim 8, wherein the assembly is in electrochemical communication with a catholyte solution.

10. The assembly of claim 9, wherein the catholyte solution comprises caustic soda.

11. The assembly of claim 10, having a cathodic voltage that is 30 mV to 400 mV less than a voltage of the assembly without the catalyst layer.

12. The assembly of claim 10, having a cathodic voltage that is 20% to 50% less than a voltage of the assembly without the catalyst layer.

13. The assembly of claim 1, wherein the fine mesh is in electrically communicative physical contact with an anode side of an ion-exchange membrane.

14. The assembly of claim 13, wherein the assembly is in electrochemical communication with an anolyte solution.

15. The assembly of claim 1, wherein the rigid backing comprises a catalytic coating consisting essentially of one or more of, iridium, osmium, palladium, rhenium, rhodium, or ruthenium.

16. The electrode of claim 1, wherein the catalytic coating of the fine mesh and/or the cushion layer further comprises one or more additive elements selected from copper, lanthanum, praseodymium, molybdenum, cerium, tantalum, titanium, molybdenum, manganese, tungsten, vanadium, indium, tin, nickel, chromium, zinc and carbon.

17. The electrode of claim 16, wherein each of the one or more additive elements is present in an amount between 0.00001% and 50.0 at. %, wherein the sum of all additive elements does not exceed 50.0 at. %.

18. The electrode of claim 15, wherein the catalytic coating of the rigid backing further comprises one or more additive elements selected from copper, lanthanum, praseodymium, molybdenum, cerium, tantalum, titanium, molybdenum, manganese, tungsten, vanadium, indium, tin, nickel, chromium, zinc and carbon.

19. The electrode of claim 18, wherein each of the one or more additive elements is present in an amount between 0.00001% and 50.0 at. %, wherein the sum of all additive elements does not exceed 50.0 at. %.

Description

III. BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention may take physical form in certain parts and arrangement of parts, embodiments of which will be described in detail in this specification and illustrated in the accompanying drawings which form a part hereof, wherein like reference numerals indicate like structure, and wherein:

(2) FIG. 1 is a side view of a typical zero-gap electrode;

(3) FIG. 2 is a graph showing that catalyzing the cushion layer has a significant effect on cell voltage;

(4) FIG. 3 is a graph showing voltage drop as a function of catalyst surface coverage;

(5) FIG. 4 is a graph showing the voltage savings as a function of current density in an in situ catalyzed zero-gap electrode versus the same electrode uncatalyzed; and

(6) FIG. 5 is a graph showing the catalytic effect as a function of current density in a cell where only the fine mesh layer is catalyzed versus a cell where all cathode components are catalyzed.

IV. DETAILED DESCRIPTION OF THE INVENTION

(7) Embodiments of the invention relate to non-platinum catalytic electrode coatings and related methods of making and using such coatings. Embodiments may also relate to electrochemical anodes and cathodes that include non-platinum catalytic electrode coatings, particularly zero-gap electrodes having a non-platinum catalyzed cushion layer.

(8) While in the past cushion layers were sometimes catalyzed by default in in situ coating processes, until now cushion layers were not specifically targeted because it was conventionally believed that they had negligible participation in the electrolytic reaction. This was a self-fulfilling prophesy because, operating under this mistaken belief, cells were manufactured with un-catalyzed cushion layers. Thus, the cushion layer did exhibit negligible activity, but this was due primarily to its lack of catalytic coating, and only to a much lesser degree due to it distance from the membrane. The teachings of the present invention indicate that conventional wisdom is wrong, that cushion layers have significant electrolytic activity when catalyzed, and that platinum-matrix catalytic layers can be replaced by non-platinum alternatives.

(9) Methods are taught herein for applying non-platinum catalyst in situ to a cushion layer as well as to other cathode components, thereby significantly increasing the electrolytically active area and lowering the cell voltage. Chlor-alkali cells are used herein as examples; however, the ordinarily skilled artisan will readily appreciate that the disclosed coatings are suitable for many other types of electrolytic cells.

(10) An electrode according to some embodiments of the invention can comprise a structure as illustrated in FIG. 1. According to FIG. 1, a zero-gap electrode 100 may include a rigid backing 130, a central cushion layer 120, and a fine mesh layer 110. While only a single layer of cushion material is illustrated in FIG. 1, the skilled artisan will appreciate that multilayers are also within the scope of the invention. The rigid backing 130 may be adapted to electrically communicate with an external circuit. For instance, the backing may include a terminal or other known structure suitable for this purpose, which the skilled artisan would readily appreciate as a matter of design choice. The cushion layer 120 may be spot welded to the rigid backing 130 and to the fine mesh 110, according to methods known in the art, thereby forming a unitary structure with operably sufficient electrical conductivity. The skilled artisan will appreciate that the invention is not limited to methods of joining the backing 130, cushion layer 120, and fine mesh 110 and that other suitable means known in the art may be substituted without departing from the scope of the invention. Moreover, while the specific structure of the fine mesh 110 may vary as set forth in detail herein, suitable structures are capable of physically contacting an ion exchange membrane without damaging the membrane. Thus, suitable fine meshes are substantially free of sharp edges and points that may perforate a membrane. Advantageously, catalytic material may be applied to the cathode components, including the cushion layer. The term catalytic material is used here to indicate that catalyst may take the form of metals, metal oxides, or mixtures thereof.

(11) Fine mesh according to some embodiments of the invention can include an electrically conductive mesh comprising a woven nickel wire mat. Not intending to indicate order of preference, the fine mesh may alternatively comprise a welded wire mesh an expanded nickel, louvered nickel, punched nickel, or any other suitable structure that permits the free flow of electrolyte and evolved gas.

(12) With respect to woven and welded wire meshes, a fine mesh mat according to the invention may have a wire diameter between 0.05 mm and 0.50 mm+/10%. Other ranges within the scope of the invention include 0.05 and 0.10 mm, 0.10 and 0.15, 0.15 and 0.20, 0.20 and 0.25, 0.25 and 0.30, 0.30 and 0.35, 0.35 and 0.40, 0.40 and 0.45, 0.45 and 0.50 mm and any operable combination thereof. With further regard to woven and/or welded mats, the fine mesh may have a strand density between 1 strand per inch and 60 strands per inch+/10%. Other strand density ranges within the scope of the invention include between 1 and 5, 5 and 10, 10 and 15, 15 and 20, 20 and 25, 25 and 30, 30 and 35, 35 and 40, 45 and 50, 50 and 55, 55 and 60 strands and any operable combination thereof.

(13) According to embodiments of the invention a fine mesh may have a thickness between 0.05 and 0.50 mm+/10%. Other ranges within the scope of the invention include 0.05 and 0.10 mm, 0.10 and 0.15, 0.15 and 0.20, 0.20 and 0.25, 0.25 and 0.30, 0.30 and 0.35, 0.35 and 0.40, 0.40 and 0.45, 0.45 and 0.50 mm and any operable combination thereof.

(14) Catalytic coatings may be applied to cushion layers either in situ or ex situ. Ex situ methods include, without limitation, thermal or plasma spray, vacuum deposition, evaporative deposition, thermal curing/bonding, electroplating and other suitable methods. In situ application can utilize electroplating, electrophoresis or other techniques relying on the electrical current in the cell. Moreover, coatings may be applied either with or without roughening the substrate. It is contemplated that roughening according to known methods may increase electrolytically active surface area and thus result in improved performance. However, roughening is not a requirement or limitation of the invention.

(15) Catalyst coatings according to the invention may have a thickness between 0.005 m and 5 m. Other thicknesses within the scope of the invention include 0.005 m and 0.010, 0.010 and 0.015, 0.015 and 0020, 0.020 and 0.025, 0.025 and 0.030, 0.030 and 0.035, 0.035 and 0.040, 0.040 and 0.045, 0.045 and 0.050, 0.050 and 0.055, 0.055 and 0.060, 0.060 and 0.065, 0.065 and 0.070, 0.070 and 0.075, 0.075 and 0.080, 0.080 and 0.085, 0.085 and 0.090, 0.090 and 0.095, 0.095 and 0.100, 0.100 and 0.150, 0.150 and 0.200, 0.200 and 0.250, 0.250 and 0.300, 0.300 and 0.350, 0.350 and 0.400, 0.400 and 0.450, 0.450 and 0.500, 0.500 and 0.600, 0.600 and 0.700, 0.700 and 0.800, 0.800 and 0.900, 0.900 and 1.000, 1.000 and 1.500, 1.500 and 2.000, 2.000 and 2.500, 2.500 and 3.000, 3.000 and 3.500, 3.500 and 4.000, 4.000 and 4.500, 4.500 and 5.000 m, and any operable combination thereof. Thicknesses may also exceed 5 m.

(16) Catalyst coatings according to the invention may have surface loadings between 5 mmol/m.sup.2 and 120 mmol/m.sup.2. Other ranges within the scope of the invention include 5 mmol/m.sup.2 and 10, 10 and 15, 15 and 20, 20 and 25, 25 and 30, 30 and 35, 35 and 40, 40 and 45, 45 and 50, 50 and 55, 55 and 60, 60 and 65, 65 and 70, 7.0 and 75, 75 and 80, 80 and 85, 85 and 90, 90 and 95, 95 and 100, 100 and 105, 105 and 110, 110 and 115, 115 and 120, and any operable combination thereof.

(17) Catalyst coatings of the invention may lower hydrogen overpotential of a zero-gap nickel cathode of a chlor-alkali membrane cell between 30 mV and 400 mV compared to the same cathode with no catalytic coating. Other ranges within the scope of the invention include 30 mV and 40 mV, 40 and 50, 50 and 60, 60 and 70, 70 and 80, 80 and 90, 90 and 100, 100 and 110, 110 and 120, 120 and 130, 130 and 140, 140 and 150, 150 and 160, 160 and 170, 170 and 180, 180 and 190, 190 and 200, 200 and 210, 210 and 220, 220 and 230, 230 and 240, 240 and 250, 250 and 260, 260 and 270, 270 and 280, 280 and 290, 290 and 300, 300 and 310, 310 and 320, 320 and 330, 330 and 340, 340 and 350, 350 and 360, 360 and 370, 370 and 380, 380 and 390, 390 and 400, and any operable combination thereof.

(18) Catalyst coatings of the invention may lower hydrogen overpotential of a zero-gap nickel cathode of a chlor-alkali membrane cell between 20% and 50% compared to the same cathode with no catalytic coating. Other ranges within the scope of the invention include 20% and 25, 25 and 30, 30 and 35, 35 and 40, 45 and 50% and any operable combination thereof.

(19) Catalyst compositions according to the invention may comprise of one or more of cobalt, copper, gold, iridium, osmium, palladium, rhenium, rhodium, ruthenium, or silver. These metals are referred to herein as catalytic metals, and as used herein they are said to be made from metal salt catalyst precursors. Additionally, catalyst compositions according to some embodiments of the invention may also contain one or more additive elements that aid or participate in the hydrogen evolution reaction such as, without limitation, copper, lanthanum, praseodymium, molybdenum, cerium, tantalum, titanium, molybdenum, manganese, tungsten, vanadium, indium, tin, nickel, chromium, zinc and carbon. According to embodiments of the invention, additive elements may be present in catalyst coatings, alone or in combination, in amounts not exceeding 50 at. %+/10 at. %, and no less than 0.00001 at. %. Other ranges within the scope of the invention include, without limitation, 0.00001 at. % to 0.00010, 0.0001-0.0010, 0.001-0.010, 0.01-0.10, 0.1-1.0, 1.0-10.0, 10.0-20.0, 20.0-30.0, 30.0-40.0, and 40.0-50.0 at. %.

(20) Suitable catalyst precursors and/or additive elements, in accordance with the invention, are soluble in the catholyte under typical in situ conditions, and/or either comprise a species or form a species in situ that is depositable on the cathode surface according to known methods such as, without limitation, electrophoresis or electroplating. As used herein, in situ conditions are those which are consistent with the ordinary operating conditions of the cell, such conditions being well-known to the person having ordinary skill in the art. In general, metal hydroxide and metal tetraamine complexes are expected to be particularly effective. In the special case of carbon as an additive element, the skilled artisan will appreciate that suitable forms in which carbon may be introduced include carbon dioxide, sodium or potassium carbonate, sodium or potassium bicarbonate, carbon monoxide, and/or methanol.

(21) Cobalt metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, tetramine (chloroaqua) cobalt (III), tetramine dichloro cobalt (III), and cobalt(II) hydroxide.

(22) Gold metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, gold(III) hydroxide and gold tetraamine complexes.

(23) Iridium metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, tetraamineiridium chloride, and iridium (IV) hydroxide.

(24) Osmium metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, tetraaminedioxoosmium (VI) chloride and osmium (IV) hydroxide.

(25) Palladium metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, palladium (II) hydroxide, and tetraamminepalladium (II) chloride monohydrate, tetraaminepalladium (II) hydroxide, tetraaminepalladium (II) tetrachloropalladate (II), tetraaminepalladium (II) oxalate and tetraaminepalladium (II) bromide.

(26) Rhenium metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, sodium perrhenate (VII) and potassium perrhenate (VII).

(27) Rhodium metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, rhodium (III) hydroxide, and tetraaminediaquarhodium (III) complexes.

(28) Ruthenium metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, ruthenium tetraamine and complexes, potassium ruthenate (VI), and sodium ruthenate (VI).

(29) Silver metal salt catalyst precursors that are suitable for producing catalyst compositions of the present invention include, without limitation, silver(I) perrhenate, and silver(I) hydroxide.

Example 1

(30) A Catalyzed Cushion Layer Significantly Lowers the Hydrogen Overpotential.

(31) Electrolysis of 1N NaOH is conducted in a beaker utilizing a platinum mesh anode and a cathode comprised of fine nickel mesh, a nickel cushion layer, and coarse nickel mesh compressed together to form a cathode sandwich. The fine nickel mesh is made from 0.127 mm diameter nickel 200 wire woven at 34 strands per inch. The cushion layer is made from nickel 200 wire with a diameter of 0.15 mm and containing 1.14 m.sup.2 of actual surface area per m.sup.2 of projected area. The coarse mesh is made from 0.625 mm thick nickel 200 expanded to have an actual surface area of 1.6 times that of the projected area. The gap between the anode and cathode is maintained at 19 mm and the electrolyte temperature is 855 C. Measurement of the cathode voltage is performed with a saturated calomel reference electrode and a lugin probe made from 1/16 diameter Teflon tubing inserted through the coarse and cushion layers and resting against the backside of the fine nickel mesh. The tubing is filled with 1N NaOH. No roughening or alteration of the nickel surfaces is performed, though it is expected that roughening would increase electrolytic activity. Voltages are recorded at a range of current densities which are calculated according to projected area.

(32) A catalytic metal according to the invention was electroplated ex situ on none, some, or all of the cathode components prior to assembly of the cathode sandwich. The following combinations were tested:

(33) TABLE-US-00001 TABLE I Compare to FIG. 2. Trial Coarse Cushion Fine A Bare Nickel Bare Nickel Bare Nickel B Bare Nickel Bare Nickel Catalyst C Catalyst Bare Nickel Catalyst D Catalyst Catalyst Catalyst

(34) Results are shown in FIG. 2 and illustrate that applying catalyst to the cushion layer significantly lowers the hydrogen evolution voltage, contrary to the result expected according to conventional wisdom. While not intending to be bound by theory, it is believed that the lower voltage is the result of more surface area evolving hydrogen which effectively lowers the current density and hence the voltage.

Example 2

(35) Hydrogen Overpotential Drops in a Membrane Cell as Catalyst Deposition, i.e. Surface Coverage, Increases.

(36) Electrolysis of 10N NaOH is conducted in a separated membrane cell utilizing an activated titanium mesh anode and a cathode comprised of fine nickel mesh, a nickel cushion layer, and coarse nickel mesh compressed together to form a cathode sandwich. The fine nickel mesh is made from 0.127 mm diameter nickel 200 wire woven at 34 strands per inch. The cushion layer is made from nickel 200 wire with a diameter of 0.15 mm and containing 1.14 m.sup.2 of actual surface area per m.sup.2 of projected area. The coarse mesh is made from 0.625 mm thick nickel 200 expanded to have an actual surface area of 1.6 times that of the projected area. The cation selective membrane is Nafion from the DuPont company. The anolyte is 1N NaOH, the catholyte is 10N NaOH and the cell temperature is 775 C. Measurement of the cathode voltage is performed with a saturated calomel reference electrode and a lugin probe made from 1/16 diameter Teflon tubing inserted through the coarse and cushion layers and resting against the backside of the fine nickel mesh. The tubing is filled with 1N NaOH. No roughening or alteration of the nickel surfaces is performed. Cathode voltages are recorded at a current density of 5.4 kA/m.sup.2 and are calculated according to projected area.

(37) During electrolysis and evolution of hydrogen from the cathode, known amounts of metal salt catalyst precursor are added to the catholyte for in situ deposition on the cathode. The addition of metal salt catalyst precursors catalyzes the cathode structure and lowers the voltage required for hydrogen evolution, i.e. the hydrogen overpotential. FIG. 3 shows how hydrogen overpotential decreases with increasing catalytic metal addition until a minimum voltage is achieved. This examples shows a drop of about 200 mV. The cathode sandwich is then dissected and the catalyst is observed on each layer of the cathode.

Example 3

(38) Catalyst Lowers Hydrogen Overpotential at all Current Densities in a Membrane Cell.

(39) The following process uses the same cell configuration as described in Example 2. Prior to addition of catalyst precursor, the voltage of a bare nickel cathode is measured against a saturated calomel reference electrode at a range of current densities. Following addition of 50 mmol/m.sup.2 of catalyst precursor to the catholyte, according to projected area, the voltage of the cathode is again measured against a saturated calomel reference electrode at the same range of current densities. The temperature of the catholyte is 851 C. FIG. 4 shows that in situ catalyst addition lowers the voltage of the cathode across the entire range of current densities where measurements are taken. Following the experiment, the cathode is disassembled and catalyst deposition is observed on all layers of the cathode.

Example 4

(40) Catalyst Lowers Hydrogen Overpotential at all Current Densities in an Undivided Cell.

(41) Electrolysis of a solution of 1N NaOH with 44 mL per liter of 8% bleach solution is conducted in a beaker utilizing a platinum mesh anode and a cathode comprised of catalytic metal electroplated fine nickel mesh, a nickel cushion layer, and coarse nickel mesh compressed together to form a cathode sandwich. The fine nickel mesh is made from 0.127 mm diameter nickel 200 wire woven at 34 strands per inch. The cushion layer is made from nickel 200 wire with a diameter of 0.15 mm and containing 1.14 m.sup.2 of actual surface area per m.sup.2 of projected area. The coarse mesh is made from 0.625 mm thick nickel 200 expanded to have an actual surface area of 1.6 times that of the projected area. The gap between the anode and cathode is maintained at 19 mm and the electrolyte temperature is 855 C. Measurement of the cathode voltage is performed with a saturated calomel reference electrode and a lugin probe made from 1/16 diameter Teflon tubing inserted through the coarse and cushion layers and resting against the backside of the fine nickel mesh. The tubing is filled with 1N NaOH. No roughening or alteration of the nickel surfaces is performed aside from the deposition of catalyst on the fine nickel mesh.

(42) Prior to adding catalyst, cathode voltages are recorded at a range of current densities calculated according to projected area. Catalyst is then plated in situ onto the cathode by adding 38 mmol/m.sup.2 of catalyst precursor while operating the cell at 5.4 kA/m.sup.2. Following the deposition of catalyst, the cathode voltage is again recorded at the same range of current densities. A plot of voltage versus current density is shown in FIG. 5 illustrating that the catalyst coating lowered the cathode voltage at all current densities, and that the voltage savings increases with current density.

(43) It will be apparent to those skilled in the art that the above methods and apparatuses may be changed or modified without departing from the general scope of the invention. The invention is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.