WO2019084416A1

WO2019084416A1 - System and method of manufacturing metal alloy composite electrodes

Info

Publication number: WO2019084416A1
Application number: PCT/US2018/057729
Authority: WO
Inventors: George H. Miley; Kyu-Jung Kim; Tapan C. PATEL; Jacob L. MEYER; Timothy P. WHEELER; Shriji B. BAROT
Original assignee: Ih Ip Holdings Limited
Priority date: 2017-10-26
Filing date: 2018-10-26
Publication date: 2019-05-02

Abstract

The presently disclosed subject matter is directed to electrodes for use in an electrolytic cell. Particularly, the disclosed electrodes comprise two or more alloys and/or intermetallic compounds constructed as microparticles or nanoparticles that provide a lattice substructure. The disclosed electrode further includes various types of defects that increase the electrode surface area. Specifically, the defects can comprise interstitial vacancies and/or dislocations that allow a multiplicity of atoms to form as a dense cluster. The dense clusters can increase the capacity for hydrogen and hydrogen isotope absorption and desorption.

Description

TITLE

SYSTEM AND METHOD OF MANUFACTURING METAL ALLOY COMPOSITE

ELECTRODES CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 62/577,326, filed October 26, 2017, the entire content of which is hereby incorporated by reference. TECHNICAL FIELD

The presently disclosed subject matter is directed to a system and method of manufacturing metal alloy composite electrodes for use in an electrolytic cell. Particularly, the disclosed electrodes include metal alloy composite particles that reversibly react with gaseous hydrogen and/or hydrogen isotopes through absorption and/or desorption.

BACKGROUND

Significant research in the generation of excess heat with hydrogen-absorbing materials has focused on electrolysis and gas-based experiments that incorporate an electrolytic cell. Particularly, electrolytic cells include a first electrode constructed from a transition metal (such as palladium or nickel), a second electrode constructed from an inert metal (such as gold or platinum), a working fluid (such as heavy water or deuterium gas), and an electrolyte (such as lithium deuteroxide). Prior art metallic electrodes that reversibly react with gaseous hydrogen and/or its isotopes are typically formed as alloys or intermetallic compounds, usually as a combination of metals with higher hydrogen affinity and non-hydrogen affinity. However, prior art metallic electrodes have a limited capacity and absorb/desorb gaseous hydrogen as a single atom to form a beta phase hydride or deuteride. It would therefore be beneficial to provide an electrolytic cell that overcomes the shortcomings of the prior art to increase the loading of hydrogen or deuterium onto a reactant electrode. SUMMARY

In some embodiments, the presently disclosed subject matter is directed to a method of manufacturing an electrode for an electrochemical cell. Particularly, the method comprises melting together about 1 -99 weight percent of a first metal and about 99-1 weight percent of a second metal, based on the total weight of the melt, through the application of heat, pressure, or both. The first metal exhibits no affinity for hydrogen and/or hydrogen isotopes and the second metal exhibits an affinity for hydrogen and/or hydrogen isotopes. The method comprises cooling the resultant melt to produce a solid form alloy electrode, wherein molecules of the first metal form a matrix that is embedded with molecules of the second metal. The method comprises producing one or more defects selected from interstitial vacancies, dislocations, or combinations thereof in the electrode to increase surface area of the alloy compared to the surface area prior to the incorporation of the defects.

In some embodiments, the first metal is selected from aluminum, gallium, indium, scandium, thallium, lead, bismuth, boron, silicon, germanium, arsenic, antimony, tellurium, polonium, palladium, and/or nickel, lithium, sodium, potassium, rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, dubnium, or combinations thereof.

In some embodiments, the second metal is selected from chromium, molybdenum, tungsten, seaborgium, manganese, technetium, rhenium, bohrium, iron, ruthenium, osmium, hassium, cobalt, rhodium, indium, meitnerium, platinum, copper, silver, gold, zinc, cadmium, mercury, or combinations thereof.

In some embodiments, the melt comprises about 1 -50 weight percent of the first metal and about 50-99 weight percent of the second metal.

In some embodiments, the defects are produced through oxidation, ball milling, gas ionization, melt spun ribbon techniques, or combinations thereof.

In some embodiments, the defects are selected from interstitial vacancies, dislocations, or combinations thereof. In some embodiments, the electrode comprises a surface area of about 5-75 m²/g.

In some embodiments, the first metal has a hydrogen affinity and/or hydrogen isotopes affinity of less than about 50 pM and the second metal has a hydrogen affinity and/or hydrogen isotope affinity of greater than about 500 pM.

In some embodiments, the melting is accomplished through arc or induction heating.

In some embodiments, the method further comprises adding about 0.1 -5 weight percent additive before, during, or after melting.

In some embodiments, the melt is cooled under an inert gas selected from one or more of argon, nitrogen, argon, helium, xenon, neon, or krypton.

In some embodiments, the electrode is fully or partially oxidized.

In some embodiments, the presently disclosed subject matter is directed to an electrode produced by the disclosed method.

In some embodiments, the alloy molecules of the electrode have a particle diameter of about 5000 micron or less or about 500 micron or less.

In some embodiments, the electrode comprises a surface area of about 5-500 m²/g or 150-400 m²/g, calculated in accordance with ASTM D3663.

In some embodiments, the presently disclosed subject matter is directed to a reactor comprising an electrolytic cell that includes an electrode produced by the disclosed method.

In some embodiments, the reactor is configured to generate heat in an amount of at least about 150% of an energy input to the electrolytic cell.

In some embodiments, the reactor is configured to generate heat in an amount of at least about 500% of an energy input the electrolytic cell.

BRIEF DESCRIPTION OF THE DRAWINGS

The previous summary and the following detailed descriptions are to be read in view of the drawings, which illustrate some (but not all) embodiments of the presently disclosed subject matter. Fig. 1 is a schematic of a method that can be used to produce a composite electrode in accordance with some embodiments of the presently disclosed subject matter.

Fig. 2 is a front plan view of a vacuum induction melting furnace that can be used in accordance with some embodiments of the presently disclosed subject matter.

Fig. 3 is a front plan view of a melt spinning apparatus that can be used in accordance with some embodiments of the presently disclosed subject matter.

Figs. 4a and 4b are front plan views of ball mills that can be used to increase the surface area of one or more metals alloys in accordance with some embodiments of the presently disclosed subject matter.

Fig. 5a is a line graph of an Ellingham Diagram of various metal oxides.

Fig. 5b is a line graph of an Ellingham and Richardson diagram of palladium and zirconium.

Fig. 6 is a transmission electron microscopy image of Pd₃₄.6Zr₆5.₄, including grain boundaries and dislocation.

DETAILED DESCRIPTION

The presently disclosed subject matter is introduced with sufficient details to provide an understanding of one or more particular embodiments of broader inventive subject matters. The descriptions expound upon and exemplify features of those embodiments without limiting the inventive subject matters to the explicitly described embodiments and features. Considerations in view of these descriptions will likely give rise to additional and similar embodiments and features without departing from the scope of the presently disclosed subject matter.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently disclosed subject matter pertains. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods, devices, and materials are now described. Following long-standing patent law convention, the terms "a", "an", and "the" refer to "one or more" when used in the subject specification, including the claims. Thus, for example, reference to "an electrode" can include a plurality of such electrodes, and so forth.

Unless otherwise indicated, all numbers expressing quantities of components, conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the instant specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the presently disclosed subject matter.

As used herein, the term "about", when referring to a value or to an amount of mass, weight, time, volume, concentration, and/or percentage can encompass variations of, in some embodiments +/-20%, in some embodiments +/-10%, in some embodiments +/-5%, in some embodiments +/-1 %, in some embodiments +/-0.5%, and in some embodiments +/-0.1 %, from the specified amount, as such variations are appropriate in the disclosed packages and methods.

The presently disclosed subject matter is directed to an electrode for use with an electrolytic cell. The term "electrode" refers to an electrical conduction device where ions and electrons are exchanged with electrolyte and an outer circuit. The disclosed electrode is constructed from one or more alloys and/or intermetallic compounds. The term "alloy" refers to a substance comprising two or more metallic elements and one or more metallic phases. The term "intermetallic" refers to a compound with one solid phase comprising two or more metallic elements, wherein the crystal structure of intermetallic compound differs from the crystal structure of the constituents.

In some embodiments, the alloys and/or intermetallic compounds of the disclosed electrode can be constructed as microparticles or nanoparticles that provide a lattice substructure. The term "microparticle" refers to a particle having a size in the micron-sized range, from about 0.1 -1000 micron. The term "nanoparticle" refers to a particle having a size in the nano range, from about 0.1 -1000 nm (0.0001 -1 micron). In embodiments where the particle is substantially spherical in shape (e.g., a microbead), the particle size refers to the diameter of the microparticle. In embodiments where the particle does not have a spherical shape, the particle size can refer to the equivalent diameter of the particle relative to a spherical particle or can refer to a dimension (length, breadth, height or thickness) of the non-spherical particle.

As illustrated in Fig. 1 , the disclosed electrode can be constructed by melting together first and second metals 100, 105 at step 110. The molten material is then cooled, and subjected to treatment to increase the surface area of the resultant product. The disclosed electrode thus includes various types of defects that increase the electrode surface area. Specifically, the defects can comprise interstitial vacancies and/or dislocations that allow a multiplicity of atoms to form as a dense cluster. Interstitial vacancies are gaps or openings in the structure of the metal matrix or embedded metals. Dislocations refer to the movement of one or more molecule from the metal matrix or embedded material to a new location. The dense clusters can increase the capacity for hydrogen and hydrogen isotope absorption and desorption. The defects can be formed through one or more of oxidation, cryogenic ball milling, and/or beta phase hydride formation, as described in more detail herein below.

The disclosed composite electrodes are constructed with a matrix formed from first metallic material 100 into which second metallic material 105 is embedded. The term "matrix" refers to an electrochemically inactive material that forms a support into which an active material is implanted. Specifically, the first metallic material (the material forming the matrix) is selected from one or more metals without an affinity for hydrogen and/or hydrogen isotopes (deuterium, protium, tritium). The second metallic material (the material embedded in the matrix) is selected from one or more metals with an affinity for hydrogen and/or hydrogen isotopes. The resultant electrodes are therefore formed from two or more materials that have different physical and/or chemical properties that are differentiated in a finished structure. As a result, the electrodes allow for the cyclic absorption and desorption of hydrogen and/or hydrogen isotopes.

A molecule with affinity for hydrogen (and/or hydrogen isotopes) specifically interacts through hydrogen bonding, Van der Waals forces, electrostatic forces, hydrophobic forces, etc. to hydrogen or the hydrogen isotope. To this end, an "affinity" refers to the non-random interaction of two molecules. In some embodiments, the strength of the interaction can be expressed quantitatively as a dissociation constant (K_D). For example, a molecule with affinity for hydrogen can have a K_D of greater than about 200, 300, 400, 500, or 600 pM. A molecule without affinity for hydrogen can have a KD of less than about 100, 50, 40, 30, 25, 10 or 5 pM. Binding affinity can be determined using standard techniques. It should be appreciated that the presently disclosed subject matter is not limited and can include molecules with an affinity outside the ranges given above.

Metals without hydrogen affinity can include (but are not limited to) the Group 6-12 metals (except palladium and nickel), such as chromium, molybdenum, tungsten, seaborgium, manganese, technetium, rhenium, bohrium, iron, ruthenium, osmium, hassium, cobalt, rhodium, indium, meitnerium, platinum, copper, silver, gold, zinc, cadmium, and/or mercury.

Metals with hydrogen affinity (e.g., the ability to attract hydrogen) include (but are not limited to) aluminium, gallium, indium, scandium, thallium, lead, bismuth, boron, silicon, germanium, arsenic, antimony, tellurium, polonium, palladium, and/or nickel, lithium, sodium, potassium, rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, and/or dubnium.

For example, in some embodiments, the electrode can comprise about 99-1 weight % of first metal 100 (e.g., zirconium) and about 1 -99 weight % of second metal 105 (e.g., palladium). Thus, the electrode can comprise at least about (or no more than about) 99, 98, 97, 96, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1 weight percent first metal 100, and at least about (or no more than about) 1 , 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99 weight percent second metal 105, based on the total weight of the electrode. In some embodiments, the disclosed electrode can comprise about 1 -50, 1 -40, 1 -30, 1 -20 or 1 -10 weight percent of the first metal and about 50-99, 60-99, 70-99, 80-99, or 90-99 weight percent of the second metal, respectively.

The disclosed composite electrodes can be formed in a variety of ways. For example, in some embodiments, first and second metals 100, 105 can be melted together to their molten (e.g., liquid) state, as illustrated in Step 110 of Fig. 1 . Melting refers to the change from solid to liquid state when exposed to sufficient heat. Any desired method can be used to melt the metallic materials, including (but not limited to) arc and/or induction heating. In some embodiments, the materials can be melted in an inactive gas environment to prevent oxidation. The term "inactive gas" refers to one or more gases that do not chemically interact with the metals or any component of the system. Suitable inactive gases can include (but are not limited to) atmospheric gases, noble gases, inert gases, carbon dioxide, and the like. In embodiments where the melting points of the first and second metals vary widely, the metal with the higher melting point can be melted first. Once melted, the metal with the lower melting point can then be added to minimize the mass loss due to evaporation. The melting points of the metals can be determined using standard techniques well known to those of ordinary skill in the art.

During melting, the metals can be housed in a heating vessel and heated using any known technique. For example, in some embodiments, a furnace can be used. The furnace can be configured as a lined vessel that houses the metals and provides the melting energy. Suitable furnace types can include (but are not limited to) electric arc furnaces, induction furnaces, cupola furnaces, blast furnaces, reverberatory furnaces, and crucible furnaces. For low temperature melting point metals (such as zinc), the vessel can be heated to about 500°C through the use of electricity, propane, and/or natural gas. For higher melting point metals, the vessel can be designed for temperatures over about 1 ,600°C through the use of electricity and/or coke.

Further, the heating vessel can be controlled to provide a desired pressure, temperature, and/or agitation (mixing) during and/or after melting.

In some embodiments, one or more additives can be added to the molten metals to provide desirable characteristics. The additive(s) can be mixed with the metals prior to melting, during melting, or after the metals have transformed to the molten state. The term "additive" refers to a solid or liquid component admixed with the metals for the purpose of affecting one or more properties of the molten metals or resultant electrode produced. The additive(s) can be present at any desired concentration. In some embodiments, the additives can be present at a concentration of about 0.1 -5 weight percent, based on the total weight of the melt. For example, the additive can be present in an amount of at least about (or no more than about) 0.1 , 0.5, 1 , 2, 3, 4, or 5 weight percent.

At step 115 of Fig. 1 , the melted metallic alloy or intermetallic compound can then be cooled using any desired method. For example, conductive plates, cooling water, reduced temperature molds, blowers, and the like can be used. In some embodiments, the melt can be cooled under an inert gas. Any suitable inert gas that does not undergo chemical reaction with the disclosed alloy and/or system can be used, including (but not limited to) argon, nitrogen, argon, helium, xenon, neon, krypton, and the like.

The resultant cooled product can be in any desired form, such as a metal ingot, rod, sponge, course powder, etc. In some embodiments, the metals of the cooled product have a size that spans a millimeter or larger scale. Accordingly, the product can be treated to maximize the surface area, as shown in Step 120 of Fig. 1. To this end, one or more of inert gas atomization, melt spun ribboning manufacturing, oxidation, and/or ball milling can be used to increase the product surface area and/or to create voids.

Particularly, inert gas atomization refers to the breakup of a molten stream of product brought about by high pressure jets of gas (e.g., inert gas). In some embodiments, the process comprises melting, refining, and degassing metal alloys in an induction melting furnace. The induction furnace can be a vacuum induction furnace, wherein the method steps occur under vacuum. Fig. 2 illustrates one embodiment of furnace 5. As shown, alloy product is melted to form refined melt 10. The melt is poured through preheated torch 15 to contact atomization nozzle 20. The atomization nozzle provides an outlet for an atomization gas, which can include one or more of nitrogen, argon, helium, etc. provided from gas source 30. In some embodiments, the atomization gas is an inert gas and/or is nonreactive with melt 10.

The melt enters the atomization nozzle and emerges from the downstream side to enter cooled chamber 35. Due to its passage through atomization nozzle 20, the melt is exposed to a plurality of plasma jets (e.g., high velocity plasma jets, such as supersonic fine plasma jets). Upon impinging on the melt, the plasma jets strip out the molten material, resulting in finely divided, spherical molten droplets. The resulting droplets are entrained by the gas into chamber 35. The droplets are cooled and freeze in-flight within the chamber, forming small, solid, and dense spherical powder particles. Powder particles 50 can be recovered at the bottom of the cooling chamber, for example in cyclone 55 and/or in filter 45, depending on the particle size distribution. The metal powder is then collected in sealed containers.

As set forth above, in some embodiments, the surface area of the metallic alloy or intermetallic compound can be increased using a melt spun ribboning process. Particularly, as shown in Fig. 3, wheel 60 is internally cooled (e.g., using water or liquid nitrogen) and rotated in one direction, as illustrated by arrow 65. A thin stream of melted alloy is then injected from nozzle 70 of crucible 75 to collide with a circumferential surface of the cooled wheel. The melt that collides with the wheel is quickly quenched (cooled) and solidified, producing ribbon-shaped alloy product 80 in a continuous manner. The ribbon-shaped alloy is termed a "melt spun ribbon." Because the melt spun ribbon is quenched at a rapid cooling rate, its microstructure includes an amorphous phase or a microcrystalline phase. In some embodiments, the method can continuously produce thin ribbons of material, with sheets several inches in width.

In some embodiments, the surface area of the metal alloy and/or intermetallic compound can be increased using a ball milling process. Specifically, the method includes the use of a cylindrical device for grinding and/or mixing materials (e.g., metal alloys, intermetallic compounds, metals). As illustrated in Figs. 4a and 4b, ball mill 90 rotates in a left/right direction and/or in a circular direction about an axis, as shown by arrows 91. The ball mill is partially filled with material 95 to be ground and grinding medium 96. In some embodiments, the grinding medium can include one or more spheres constructed from a material with superior mechanical and/or tribological properties compared to milled material 95. In use, as the ball mill rotates, the grinding medium is thrust against the interior. As a result, the size of material 95 is reduced.

In some embodiments, oxidation can be used to reduce the surface area of the electrode material. The term "oxidation" refers to the loss of electrons or an increase in oxidation state by a molecule, atom, or ion. The produced material can be fully or partially oxidized. When fully oxidized, both the first and second metals of the alloy show full mass gain from oxidation. When partially oxidized, only first metal 100 (e.g., without hydrogen affinity, the more stable metal) is oxidized, and the second metal remains unoxidized.

To achieve full oxidation, the alloy can be heated under an atmosphere comprising oxygen until a stable oxide is formed for both metals of the electrode. In some embodiments, the fully oxidized particles can be placed in a pressure chamber and exposed to an atmosphere of at least 24.7 psi (e.g., 24-40 psi). Because it is more stable, first metal 100 remains fully oxidized. In addition, because they are less stable, the oxides of second metal 105 are reduced to produce water as a reaction byproduct. For example, in the case of PdOZrO₂ alloy materials, the pressurization results in the reduction of palladium oxide (PdO) to palladium (Pd), and produces water, while zirconium dioxide (ZrO₂) remains as a matrix material for the reduced palladium.

In some embodiments, the alloy materials can be selectively oxidized. Particularly, the alloy can be heated under an atmosphere comprising oxygen until a stable oxide is formed in first metal 100 (e.g., the metal without affinity for hydrogen). The second metal therefore remains unoxidized.

In some embodiments, an Ellingham diagram can be used to determine the partial pressure of oxygen (P02) that exists in equilibrium with a given metal at a given temperature. One embodiment of an Ellingham diagram is illustrated in Fig. 5a. As shown, the x-axis represents temperature (°C) and the y-axis represents the free energy of formation of the oxide. Curves in the Ellingham diagrams for the formation of metallic oxides are shown as straight lines with a positive slope. The slope is proportional to AS (change in entropy), which is fairly constant with temperature. The lower the position of a metal line in the Ellingham diagram, the greater the stability of its oxide. For example, the line for Al (oxidation of aluminum) is shown to be below the corresponding line for iron (formation of Fe₂O₃). The stability of metallic oxides decreases with a corresponding increase in temperature. If the curves for two metals at a given temperature are compared, the metal with the lower Gibbs free energy of oxidation on the diagram will reduce the oxide with the higher Gibbs free energy of formation. For example, metallic aluminum can reduce iron oxide to metallic iron, the aluminum itself being oxidized to aluminum oxide. The greater the gap between any two lines, the greater the effectiveness of the reducing agent corresponding to the lower line.

For example, the Ellingham diagram can be used to determine the appropriate CO/CO₂ ratio for a buffering gas phase at a selected reaction temperature for a selected metal oxide. The oxygen partial pressure is taken as 1 atmosphere and all of the reactions are normalized to consume one mole of O₂. To use the diagram to determine the ration of CO/CO₂ that can reduce the oxide to metal at a given temperature, the user can locate the desired reaction temperature along the x-axis of the diagram. The curve corresponding to the oxidation line of interest is then identified. The point where the oxidation line intersects the temperature line is then determined. The user then draws a straight line from the "C" on the left axis of the diagram through the intersection of the oxidation line and the temperature line and continues it through the CO/CO₂ ratio scale. The CO/CO₂ ratio is then read from the scale where the line intersects it. This is the minimum ratio that will reduce the selected oxide. Ratios of CO/CO₂ above the minimum ratio will result in a stable oxide composition. Ratios below the minimum will favor the reactants.

In some embodiments, an Ellingham-Richardson diagram can be used to identify metals that will deposit under particular conditions, as illustrated in Fig. 5b. As shown, the diagram is a plot of the energy versus temperature for a variety of oxidation reactions. For example, when palladium (Pd) and zirconium (Zr) are selected and the PdZr alloy is heated at 553K (280°C), the Zr portion of the alloy is oxidized to form Zr0₂ with the ambient of oxygen partial pressure less than 10^"11 atm to higher than 10^"93. The method therefore produces the composite structure of Pd embedded on a ZrO₂ (zirconia) matrix.

In some embodiments, more than one technique can be used to increase the surface area of the composite electrode. For example, the product from melt spun ribboning and/or oxidized product can be subsequently reduced in particle diameter by a process of ball milling similar to the method described herein above. In some embodiments, the particle diameter of the alloy molecules in the resultant electrode are about 5000 micron or less, such as about 5000-0.1 micron, 4500-10 micron, 4000-100 micron, 3500-250 micron, 3000-400 micron, or about 2500-500 micron. It should be appreciated that the presently disclosed subject matter is not limited and the alloy materials can have a particle size greater or less than the range given above.

In some embodiments, the surface area of the resultant alloy electrode is about 5-75 m²/g (e.g., about 10-70, 11 -65, 12-60, 13-55, 14-50 m²/g). The term "surface area" refers to the external surface of a particle (e.g., surface area/gram when used with a plurality of particles such as powder). In some embodiments, the surface area can be measured by the BET (Brunauer, Emmett, and Teller) technique and/or ASTM D3663, the contents of which are hereby incorporated by reference. It should be appreciated that electrodes with a surface area greater or lesser than the range set forth above are also included within the scope of the presently disclosed subject matter.

It should be appreciated that at various stages, the disclosed method can be probed by x-ray diffraction, scanning electron microscopy, and/or transmission electron microscopy. Particularly, x-ray diffraction is a method that employs the scattering of x- rays by the regularly spaced atoms of a crystal. X-ray diffraction is useful in identifying and characterizing compounds based on their diffraction pattern. Scanning electron microscopy techniques can be used to produce images of a sample by scanning the surface with a focused beam of electrons. The electrons interact with atoms in the sample, producing various signals that contain information about the surface topography and composition of the sample. Transmission electron microscopy techniques include transmitting a beam of electrons through a specimen to form an image. The image is formed from the interaction of the electrons with the sample as the beam is transmitted through the specimen. Such methods are well known to those of ordinary skill in the art.

The disclosed method therefore produces composite electrodes comprising a first metallic material configured as a matrix, and a second metallic material embedded within the matrix. The resultant electrode includes a plurality of defects, such as interstitial vacancies and/or dislocations that result from one or more of inert gas atomization, oxidation, melt spun ribboning manufacturing, and/or ball milling. The defects therefore allow a multiplicity of atoms to form as a dense cluster. The dense clusters can increase the capacity for hydrogen and hydrogen isotope absorption and desorption. Accordingly, the produced electrodes can be used to generate increased heat and energy during electrolytic reactions when compared to prior art electrodes.

Further, many industrial applications require the loading of large amounts of hydrogen or deuterium into the electrode structure during an electrochemical reaction. The loading of hydrogen requires that hydrogen first adsorb onto the electrode metal surface before diffusing into the structure. A large surface-to-volume ratio would substantially increase the number of hydrogen atoms adsorbed on an electrode surface with potential to diffuse into the bulk.

The presently disclosed subject matter further includes a reactor configured as a closed electrolytic cell that provides for increased hydrogen or deuterium loading into a reactant electrode. Particularly, oxygen is released at the electrolytic cell anode while deuterium or hydrogen ions migrate towards the cathode. The surge of ions bombards the cathode, resulting in dense hydrogen or deuterium loading. As a result, heat in excess of the energy input to the cell is generated (e.g., 1 .5, 2, 2.5, 3, 3.5, 4, 4.5, or 5x the energy input). The presently disclosed subject matter therefore is directed to an electrolytic cell that allows for the increased loading of hydrogen and/or deuterium onto the associated electrode (e.g., cathode). As a result, of the high loading ratio of hydrogen and/or deuterium and heat is produced which can be harnessed and used. Particularly, the increased loading results in the generation of heat in excess of the energy input to the cell. The disclosed electrolytic cell can therefore be used as an effective and improved power generator.

The above description is intended to be illustrative and not limiting. Various changes and modifications in the embodiment described herein may occur to those skilled in the art. Those changes can be made without departing from the scope and spirit of the invention.

EXAMPLE

The following Example has been included to provide guidance to one of ordinary skill in the art for practicing representative embodiments of the presently disclosed subject matter. In light of the present disclosure and the general level of skill in the art, those of skill can appreciate that the following Example is intended to be exemplary only and that numerous changes, modifications, and alterations can be employed without departing from the scope of the presently disclosed subject matter. EXAMPLE 1

Production of Composite Matrix Electrode

Palladium and zirconium metals were obtained as starting materials. The metals were melted together, and then a melt-spun ribbon manufacturing method was used to produce nano-crystalline material. Particularly, a thin stream of melted palladium and zirconium alloy materials were melted and dripped onto the cooled wheel. The alloy was then rapidly solidified, producing a metal alloy ribbon.

The alloy ribbon was then heated under an atmosphere containing oxygen until a stable oxide was formed for both metals.

The material was placed into a pressure chamber and exposed to a pressure of at least 24.7 psi. The stable oxides remained fully oxidized, but the less stable oxides were reduced and produced water as a reaction byproduct. The hydrogen pressurization resulted in a reduction in PdO to Pd, and produced H₂O, while ZrO2 remained as a matrix material for the reduced Pd. As shown in Fig. 6, the crystallite size was measured at 10 nm via powder x-ray diffractometry with transmission electron microscopy in agreement with the value, translating to a grain boundary type defect volume of 5.07 x 10^"8 m³/g. In addition, the dislocation defect density was assessed by transmission electron microscopy.

Claims

CLAIMS What is claimed is:

1 . A method of manufacturing an electrode for an electrochemical cell, the method comprising:

melting together about 1 -99 weight percent of a first metal and about 99- 1 weight percent of a second metal, based on the total weight of the melt, through the application of heat, pressure, or both, wherein the first metal exhibits no affinity for hydrogen, hydrogen isotopes, or both and wherein the second metal exhibits an affinity for hydrogen, hydrogen isotopes, or both;

cooling the resultant melt to produce a solid form alloy electrode, wherein molecules of the first metal form a matrix that is embedded with molecules of the second metal;

producing one or more defects selected from interstitial vacancies, dislocations, or combinations thereof in the electrode to increase surface area of the alloy compared to the surface area prior to the incorporation of the defects.

2. The method of claim 1 , wherein the first metal is selected from aluminum, gallium, indium, scandium, thallium, lead, bismuth, boron, silicon, germanium, arsenic, antimony, tellurium, polonium, palladium, and/or nickel, lithium, sodium, potassium, rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, dubnium, or combinations thereof.

3. The method of claim 1 , wherein the second metal is selected from chromium, molybdenum, tungsten, seaborgium, manganese, technetium, rhenium, bohrium, iron, ruthenium, osmium, hassium, cobalt, rhodium, indium, meitnerium, platinum, copper, silver, gold, zinc, cadmium, mercury, or combinations thereof.

4. The method of claim 1 , wherein the melt comprises about 1 -50 weight percent of the first metal and about 50-99 weight percent of the second metal.

5. The method of claim 1 , wherein the defects are produced through oxidation, ball milling, gas ionization, melt spun ribbon techniques, or combinations thereof.

6. The method of claim 1 , wherein the defects are selected from interstitial vacancies, dislocations, or combinations thereof.

7. The method of claim 1 , wherein the electrode comprises a surface area of about 5-75 m²/g.

8. The method of claim 1 , wherein the first metal has a hydrogen affinity, hydrogen isotope affinity, or both of less than about 50 pM and the second metal has a hydrogen affinity, hydrogen isotope affinity, or both of greater than about 500 pM.

9. The method of claim 1 , wherein the melting is accomplished through arc or induction heating.

10. The method of claim 1 , further comprising adding about 0.1 -5 weight percent additive before, during, or after melting.

1 1 . The method of claim 1 , wherein the melt is cooled under an inert gas selected from one or more of argon, nitrogen, argon, helium, xenon, neon, or krypton.

12. The method of claim 1 , wherein the electrode is fully or partially oxidized.

13. An electrode produced by the method of claim 1 .

14. The electrode of claim 13, wherein the alloy molecules have a particle diameter of about 5000 micron or less.

15. The electrode of claim 13, wherein the alloy molecules have a particle diameter of about 500 micron or less.

16. The electrode of claim 13, comprising a surface area of about 5-500 m²/g, calculated in accordance with ASTM D3663.

17. The electrode of claim 13, comprising a surface area of about 150-400 m²/g, calculated in accordance with ASTM D3663.

18. A reactor comprising an electrolytic cell that includes the electrode produced by the method of claim 1 .

19. The reactor of claim 18, configured to generate heat in an amount of at least about 150% of an energy input to the electrolytic cell.

20. The reactor of claim 18, configured to generate heat in an amount of at least about 500% of an energy input the electrolytic cell.