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WO1994014163A1 - Methodes de formation de films sur des cathodes - Google Patents

Methodes de formation de films sur des cathodes Download PDF

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Publication number
WO1994014163A1
WO1994014163A1 PCT/US1993/011754 US9311754W WO9414163A1 WO 1994014163 A1 WO1994014163 A1 WO 1994014163A1 US 9311754 W US9311754 W US 9311754W WO 9414163 A1 WO9414163 A1 WO 9414163A1
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WO
WIPO (PCT)
Prior art keywords
cathode
electrolyte
deuterium
film
cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1993/011754
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English (en)
Inventor
Michael C. H. Mckubre
Romeu C. Rocha-Filho
Stuart I. Smedley
Francis L. Tanzella
Steven Crouch-Baker
Joseph Santucci
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Electric Power Research Institute Inc
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Electric Power Research Institute Inc
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Publication date
Application filed by Electric Power Research Institute Inc filed Critical Electric Power Research Institute Inc
Priority to AU57388/94A priority Critical patent/AU5738894A/en
Publication of WO1994014163A1 publication Critical patent/WO1994014163A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21B—FUSION REACTORS
    • G21B3/00—Low temperature nuclear fusion reactors, e.g. alleged cold fusion reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/10—Nuclear fusion reactors

Definitions

  • This invention relates to methods for forming films on 5 cathodes, particularly films for facilitating electrochemical charging of metals and alloys with isotopes of hydrogen (H) .
  • the formation of compounds involving hydrogen isotopes in 10 combination with certain metals and alloys is important because these compounds may be used for the storage of hydrogen isotopes and as battery electrodes. Such storage of hydrogen is useful any time one wishes to subsequently oxidize the hydrogen to produce energy, e.g., for 15 transportation or in a fuel cell.
  • the application of this invention to battery electrodes can. be for vehicle propulsion batteries and alternatives to nickel cadmium batteries.
  • ⁇ 20 is a known method for producing these so-called "hydrogen storage alloys".
  • the formation of films on the metal cathodes can be important, as loading may be affected by the film.
  • the formation of films on palladium cathodes can be important because excess power evolution has been observed during the electrochemical loading of the hydrogen isotope deuterium into palladium cathodes, and this loading may be affected by the film. Such excess power evolution has become known .collectively under the generic title of "cold fusion". The precise origin of the evolved energy is presently open to some debate, and the conditions under which it is reproducibly obtained have not hitherto been defined.
  • a method of forming a film (10) on the surface of a cathode (7) to facilitate the loading of an isotope of hydrogen into the cathode (7) is immersed with an anode
  • Electrodes (7) , (9) in an electrolyte (5) containing an isotope of hydrogen and conducting ions, and both electrodes (7) , (9) are connected to a current source (11) for promoting electrolysis and providing energy.
  • Conducting ions may be formed by the inclusion of LiOH or LiOD or LiOT in the electrolyte.
  • the addition of further elemental species or compounds to the electrolyte promotes the formation of the film (10) , and this film (10) enhances the charging of the cathode (7) with the isotope of hydrogen from the electrolyte (5) .
  • the preferred embodiments described below are concerned with the specific example of the charging of a palladium cathode (7) with deuterium (D) .
  • FIG. 1 is a partly schematic diagram of an electrolysis system 1 generic to the specific examples of apparatus for carrying out the steps of the present invention
  • FIG. 2 is a perspective diagram of an example of the electrolysis system 1 of FIG. 1, showing two gas permeable anodes 51 and thin film cathode 52;
  • FIG. 3 is a partly schematic diagram of an example of the electrolysis system 1 of FIG. 1, including metal cup 53;
  • FIG. 4 is a front cross-sectional view of electrolysis cell 22 described in Example 1 herein;
  • FIG. 5a is a front view of electrolysis cell 40 described in Example 2 herein;
  • FIG. 5b is a front cross-sectional view of electrolysis cell 40 described in Example 2 herein;
  • FIG. 6 is a front cross-sectional view of electrolysis cell 67 described in Example 3 herein;
  • FIG. 7 is a partial cross-sectional view of a cathode 7 which may be used in all examples illustrated herein.
  • FIG. 1 shows a schematic diagram of electrolysis system 1 suitable for practicing the method of the present invention, for loading deuterium into a palladium cathode 7.
  • Electrolysis system 1 includes container 3 filled with electrolyte 5. The system 1 may be enclosed in a pressurized or sealed enclosure 2, which may also serve as a heat exchanger or may comprise various heat exchange devices, well known in the art, for extracting and transferring heat from the system.
  • the electrolysis system 1 also includes two electrodes 7,9 at least partially immersed in electrolyte 5.
  • a current source 11 is connected between electrodes 7,9 to generate a flow of ions within electrolyte 5 between the two electrodes 7,9.
  • a voltage measuring device 4 indicates the potential difference between the electrodes 7,9.
  • Cathode 7 preferably is constructed of a metallic bulk region or rod 6 having an outer layer of palladium, and anode 9 is constructed of platinum, palladium, or some stable non-elemental metallic conductor material.
  • palladium is the preferred surface material for use in the cathode 7, other materials such as palladium alloys are suitable substitutes.
  • the bulk region may be constructed of metal having a low deuterium permeability, such as copper.
  • the surface of cathode 7 preferably comprises a metal 8 having a crystal structure such that roughly polyhedral spaces are enclosed by the metal atoms in the crystal lattice.
  • a metal 8 having a crystal structure such that roughly polyhedral spaces are enclosed by the metal atoms in the crystal lattice.
  • palladium has a face- centered cubic crystal structure with roughly octahedral interior spaces. Deuterium atoms can occupy these sites.
  • the palladium structure 8 thus acts as a storage medium for deuterium.
  • this association of deuterium within the palladium host material causes a phenomenon which results in the release of heat.
  • the purpose of the electrolysis system 1 is to cause deuterium to be drawn to the negatively biased cathode 7 in order to load the metal 8 with deuterium.
  • FIG. 1 shows a system 1 having a single electrolysis cell 12 comprising anode 9 and cathode 7. Alternatively, a plurality of such cells 12 may be connected together.
  • the palladium cathode may be fabricated, either in the form of a Pd rod electrode 7, or in the form of a Pd layer 8 electrodeposited onto a Cu rod 6.
  • the bulk Pd should be of high purity, and typically it is annealed in a vacuum furnace at 800°C for three hours and then allowed to cool in 1 atm. of D 2 gas or argon. The purpose of the heat treatment is to volatilize impurities from the layer 8, and to anneal out crystal imperfections.
  • Cooling the metal in a D 2 atmosphere facilitates partial loading of the metal 8 with deuterium gas, while avoiding the mechanical stress induced in crossing the two-phase miscibility gap. It is important at all stages of treatment to minimize stresses that may lead to cracking of the palladium deuteride (PdD x ) , since high loading cannot be attained or maintained by electrochemical means if cracks propagate to the surface of the metal 8.
  • PdD x palladium deuteride
  • High temperature gas loading also helps prevent the ingress of unwanted 0 2 and H 2 0 when, for short times, cathode 7 is exposed to the atmosphere. Oxidation of the surface of cathode 7 by 0 2 or H 2 0 reduces the ability of Pd to absorb D. In the case that the Pd is required to absorb only D, hydrogen produced by corrosion of Pd in H 2 0 may absorb into sites that D otherwise could occupy.
  • the Pd surface is etched in deuterated aqua regia and then rinsed in D 2 0. This process removes any oxide film from the surface of the metal 8 and aids loading by enhancing the kinetics of D adsorption-desorption.
  • the electrolyte 5 of choice is LiOD.
  • LiOD is simple to prepare, and yields products of electrolysis which are nearly 100% D 2 and 0 2 .
  • solution 5 is formed by reacting pure Li metal or Li 2 0 with D 2 0 of high isotopic purity in an inert gas environment.
  • cathode 7 In electrochemical cells 12 designed for loading deuterium gas into cathode 7, it is important to provide a uniform current over as much of the surface of cathode 7 as possible.
  • the deuterium ions which dissolve into the metal 7 are in a state of dynamic equilibrium with the gas phase of deuterium, and the transfer of surface adsorbed molecules to the absorbed state is rapid and reversible.
  • metal 7 will charge with the gas as long as the inward flux of deuterium ions is greater than the outward flux of deuterium gas.
  • cathode 7 may load unevenly, allowing the deuterium entering from the areas of high current density, and presumably high loading, to leak away to the areas of low current and presumably low loading.
  • potential sensing and current contacts 15,43 must be placed at the end of cathode 7.
  • cathode 7 can be loaded with D 2 depending on the surface conditions. Materials which deposit on cathode 7 as a result of prolonged electrolysis can severely affect the rate of ingress of gas into the metal 7, and, consequently, the degree of loading. Because of this, it is necessary to be careful about the choice of anode 9 and cell container 3 materials. Quartz glass and polytetrafluoroethylene (PTFE) are examples of suitable container 3 materials. For the same reason, anode 9 metals other than Pt or Pd should be avoided; stable electronically conductive non-elemental metallic anodes 9 are suitable.
  • All electrochemical cells 12 contain an anode 9 and a cathode 7.
  • the predominant cathode 7 reaction of the present invention is the reduction of D 2 0.
  • the anode 9 reaction is a mixture of two reactions:
  • the relative contributions of these to the anode 9 current are determined by the kinetics of each reaction. If the predominant anode 9 reaction is described by Eq. [1] , then the minimum cell voltage measured by the voltage meter 4 will be 1.27 volts at room temperature, after deuterium loading has occurred. When the minimum cell 12 voltage 4 is applied, there is no net electrochemical current in the cell. Under operating conditions, increased values of the electrochemical current are required. As current from the source 11 is increased, the cell 12 voltage 4 rises rapidly due partly to the overvoltage required for oxygen evolution described in Eq. [1] . On the other hand, if the reaction of Eq. [2] predominates, then the minimum cell 12 voltage 4 is 0 volts, after deuterium loading has occurred.
  • the first advantage is that the electrolysis system 1 can be operated under reducing conditions (i.e. absence of free oxygen) .
  • reducing conditions i.e. absence of free oxygen
  • the cathode 7 surface will react with the oxygen to produce an oxide layer which acts as a barrier for deuterium transport across the electrolyte 5/metal 7 interface. This is not conducive to the achievement of a high D/Pd atomic ratio. Generally speaking, a high D/Pd ratio is desirable.
  • the technique disclosed herein embodies several features which promote the Eq. [2] reaction at anode 9.
  • the Eq. [2] reaction is kinetically very fast, and even at low current densities is diffusion controlled; whereas the Eq. [1] reaction cannot be diffusion controlled for an electrolyte 5 that contains mostly D 2 0.
  • a method of achieving this enhancement is by increasing the concentration of D 2 in electrolyte 5.
  • the D 2 concentration in electrolyte 5 can be increased by exposing electrolyte 5 to high pressure D 2 .
  • Other ways of increasing the supply of D 2 to the anode 9 surface are by utilization of gas permeable anodes 51 (FIG.
  • the gas permeable electrode 51 shown in FIG. 2 is a porous structure that significantly increases the three phase contact area between the deuterium, the electrolyte 5, and the metal phase of anode 51.
  • Another way to increase the supply of deuterium to the anode 9/electrolyte 5 interface is to contain electrolyte 5 in a metal cup 53, that is highly permeable to deuterium, and to suspend cup 53 in high pressure deuterium gas 54, as shown in FIG. 3.
  • Metallic cup 53 serves as an anode through which current introduced by current source 45 can cause electrolyte 47 ions and D 2 0 to interact with cathode 52.
  • the high pressure deuterium gas 54 surrounding cup 53 maintains a high concentration of deuterium at the anode 53/electrolyte 47 interface and promotes the Eq. [2] reaction described above.
  • electrolysis system 1 Apart from the ability to operate under pressure, enclosing electrolysis system 1 in a sealed enclosure 2, 49 has several other advantages.
  • the electrolyte 5,47 is retained, which avoids the need for replenishment of D 2 0; and the system 1 is sealed from substances (such as H 2 0) that are deleterious to high deuterium loadings and excess heat production.
  • cathode 7 should be pre-charged at a moderate current density (between 10 and 100 mA/cm 2 ) for a time corresponding to three or more diffusion periods.
  • a diffusion period is represented approximately by x 2 /D, where x is the thickness of the metal layer 8, and D is the average chemical diffusion coefficient of deuterium in the metal 8.
  • currents of between 10 mA/cm 2 and 100 mA/cm 2 are typically used for a time of between 3 days and 10 days. If the cathode 7 preconditioning and electrolyte 5 conditions are as described above, the average atomic ratio (D/Pd) generally achieved in the steady state will be between 0.8 and 0.95.
  • a high loading ratio is important for the initiation of heat generation. Ratios of at least 0.8 (preferably at least 0.9) are required. A D/Pd ratio of unity or higher is even better.
  • the loading can be determined by measuring the resistance of cathode 7, as discussed below.
  • a film 10 on the solution side of the cathode 7/electrolyte 5 interface.
  • Aluminum (Al) introduced as an additive species to electrolyte 5 has been observed to further promote this film 10 formation.
  • Si and B are satisfactory additive species to electrolyte 5.
  • other elements believed to promote film 10 formation include Ba, Ca, Cu, Fe, Li, Mg, Ni, Sc, Ti, V, Y, and Zr.
  • the film 10 is believed to be gelatinous in form, and therefore of an ill-defined thickness, during electrolysis. After completion of the process, only a dehydrated version of the film 10 can be observed and tested.
  • This dehydrated version of the film 10 can have a thickness of approximately 1 micron.
  • the composition of the film 10 derives from the additive species as well as elements from components involved in the process.
  • the composition of the film 10 in its gelatinous form is impossible to determine, but the composition of the dehydrated version of the film 10 has been determined to be approximately 10 wt% Pt, 2 wt% Si, 1 wt% Al, 1 wt% Na, and unknown percentages of C and 0, in a specific embodiment described in Example 3.
  • Time must be provided for Li and the additive species to diffuse and electromigrate into the Pd solid 7 from electrolyte 5; and for minority element segregation to occur by diffusion within the beta-phase PdD x and by electromigration within the metal phase.
  • Film 10 formation through the addition of elemental species to electrolyte 5 results in improved absorption of deuterium into the palladium 7.
  • This film 10 is believed to improve absorption by several mechanisms.
  • the film 10 serves as a deuterium ion (D + ) conductor to facilitate the transport of desirable species (D + ) to the Pd layer 8 while selecting against the transport of electrolyte 5 impurity cations that may deposit onto the surface of cathode 7.
  • Such deposited species may prevent D absorption by acting as an impermeable layer or by catalyzing the alternate process of recombination (D ads + D ads ⁇ D 2 ,gas) .
  • film 10 serves to hinder recombination by blocking molecular adsorption sites and preventing atomic and molecular diffusion on the surface of cathode 7.
  • film 10 serves to prevent the nucleation of D 2 gas bubbles, thereby increasing the effective pressure of deuterium and the limit of loading (D/Pd) .
  • deloading at these sites is reduced or prevented.
  • a cathode 7 that is adequately loaded for a sufficient period of time and subjected to a sufficient interfacial current density will yield excess heat.
  • High currents are desirable for three reasons: to attain high loading, to attain D fluxes in the metal phase, and to permit a film 10 to form appropriately at the cathode 7 and electrolyte 5 interface.
  • a vessel 21 is constructed of copper and has a cylindrical sleeve shape with an internal surface of platinum, which acts as the anode 19. Positioned along the central axis of vessel 21 is palladium cathode 31. Cathode 31 is cylindrical in shape and contains voltage connectors 15 on each end. Separating cathode 31 and anode 19 is electrolyte 27 consisting of LiOD in D 2 0. A temperature sensor 32 penetrates vessel 21 to contact cathode 31.
  • the electrolyte 27 is exposed only to the materials palladium, platinum and polytetrafluoroethylene
  • PTFE PTFE
  • Palladium cathode 31 is a 7mm dia., 4 cm long Pd rod, machined from a twice-melted pure Pd source. A 2mm threaded hole 30 is machined in the center of the side of cathode 31 to accept temperature sensor 32. Once machined, cathode 31 is vacuum annealed at 800°C for two to three hours and cooled in one atmosphere of D 2 . Cathode 31 is next dipped in aqua regia for 20 seconds and rinsed with D 2 0 immediately before cell 22 assembly.
  • the 0.1M LiOD electrolyte 27 is prepared by adding 0.035g Li metal (Aesar 99.9% used as received) to 50 ml D 2 0 (Aldrich 99.9 atom % D, as received) . This preparation is carried out under a nitrogen atmosphere, preferably immediately prior to use.
  • Cell 22 is assembled with minimum exposure to air or H 2 0 by threading the ends of cathode 31 into one of two end-pieces 25. This end-piece 25 is then sealed into the body of vessel 21 using a PTFE sealing ferrule and a Cu nut 24. An opposing end-piece 25 is similarly threaded onto cathode 31 in vessel 21 and sealed in place. A 2mm Pt coated Cu tube 29 containing temperature sensor 32 is passed through the side wall of vessel 21 and sealed into threaded hole 30 in cathode 31.
  • Exposed areas of end-pieces 25 and temperature sensor tube 29 are coated with epoxy and PTFE to electrically insulate them from electrolyte 27. Electrical connections are made to voltage connections 15 and current connections 23 to measure the Pd resistance and introduce the electrolyzing current.
  • a 1/8" outside diameter Cu gas inlet 17, extending to an external manifold, is sealed to a threaded hole on the wall of vessel 21 above the level of electrolyte 27. Vessel 21 is maintained in a constant temperature water bath at 7°C and pressurized to 300 psig with D 2 via inlet 17.
  • Measurements of cell 22 voltage and Pd cathode 31 temperature are made and recorded by computer every two minutes. Palladium resistance measurements are made manually by passing up to 10A of alternating current between cathode current connections 23, and then measuring the voltage drop along cathode 31 between voltage connections 15. An anode connection 16 is attached to the vessel 21.
  • the cathode current connections 23 supply current to the system while the voltage connections 15, which have no current running through them, measure the potential difference in the system. As one skilled in the art will recognize, measurement of the potential difference by use of the cathode current connections 23 would be incorrect due to the voltage contribution of the resistance in the cathode current connections 23.
  • Pressure is read on a mechanical pressure gauge on the external manifold and recorded manually. As the P 2 diffuses into the Pd cathode 31, it is compensated by adding D 2 to maintain a constant cell 22 pressure.
  • the foregoing apparatus is useful for performing a calorimetry experiment, in which one seeks to compare the known and measured sources of input energy or power to the system with the observed output energy or power.
  • the difference between the output energy and input energy is defined as the "excess heat" .
  • the containment vessel 36 is constructed of Ni and has a cylindrical sleeve shape with an internal surface of Pt, which acts as the anode 41. Positioned along the central axis of vessel 36 is palladium cathode 39. Cathode 39 is cylindrical in shape and contains cathode current connectors 44 and voltage connectors 43 on opposing ends. An anode connection 47 is attached to the outside of the vessel 36. Separating the cathode 39 and anode 41 is the electrolyte 38, consisting of LiOD in D 2 0. A reference electrode 42 penetrates vessel 36 to contact electrolyte 38.
  • the electrolyte 38 is exposed only to the materials palladium, platinum, and polytetrafluoroethylene (PTFE) .
  • the inner surface of the Ni vessel 36, as well as the surfaces of the Ni fittings exposed to the electrolyte 38, are coated with a 25 micron Ni film via an electroless plating method and then with a 5 micron film of Pt via an electroplating method. This Pt coating serves as anode 41. All metal and PTFE cell surfaces are solvent cleaned and rinsed. The Pt coated surfaces are further washed with aqua regia and rinsed with D 2 0.
  • the Pd cathode 39 is a 3mm dia., 5 cm long Pd rod (4.5 mm exposed to electrolyte 38) , machined from a 1/8" pure Pd wire. Cathode 39 is threaded 2.5mm on each end. Cathode 39 is then solvent cleaned, vacuum annealed at 800°C for two to three hours, slowly cooled in one atmosphere of D 2 , and maintained in the D 2 until cell 40 is ready for assembly.
  • the 1.0 M LiOD electrolyte 38 is manufactured by adding 0.175g Li metal to 25 ml D 2 0. This procedure is carried out under a nitrogen atmosphere, and electrolyte 38 is prepared immediately prior to use.
  • a Ni cathode 39 of shape and size identical to palladium cathode 39 is temporarily assembled into vessel 36 with 20 ml of electrolyte 38.
  • the Ni cathode 39 is held at 0.5 mA cathodic with respect to the cell wall anode 41 for three hours to help remove impurities from electrolyte 38.
  • This pre-electrolysis is carried out under a 40 psig pressure of N 2 before the Ni cathode 39 is removed and discarded.
  • An external 180 ohm steel sheathed heater (.04" diameter, 72" long) is wound in a groove 37 machined around the outside of vessel 36.
  • Cell 40 is assembled immediately after pre-electrolysis with minimum exposure to air or H 2 0.
  • Cathode 39 is threaded into one coated Ni end-piece 46 and inserted into vessel 36.
  • the other end-piece 46 is then threaded onto cathode 39 in vessel 36 as above.
  • a 3mm Ni electrode 42 coated with Pt (to be used as a pseudo- reference electrode) is sealed into the threaded hole 34 in the middle of vessel 36.
  • a 1/8" outside diameter external Ni tube 48, extending out of vessel 36, is sealed to the pressure inlet 35, above the level of electrolyte 38.
  • the vessel 36 is pressurized to 1000 psig with D 2 via tube 48.
  • Cell 40 is allowed to operate for two hours to ascertain the integrity of cell 40.
  • Cathode 39 is held at 20 mA cathodic for approximately one hour.
  • the current is increased in 10mA steps to 50 mA over a two hour period.
  • D 2 diffuses into the cathode 39, it is compensated by adding D 2 via tube 48 to maintain a constant cell 40 pressure.
  • FIG. 6 shows a cell 67 which operates at approximately atmospheric pressure.
  • the vessel 69 is constructed of Al and has a cylindrical sleeve shape with an internal surface of PTFE. Positioned along the central axis of vessel 69 is palladium cathode 55. A cathode current connection 83 and an anode connection 85 are attached. The electrolysis portion of the cell 67 is exposed only to the materials palladium, platinum, quartz glass, and PTFE.
  • Anode 65 consists of an approximately 1. Om long piece of 0.5mm dia. Pt wire wound around a cage 73 of five quartz glass rods held in place by two PTFE discs 75. The wire 65 is held in place by attachment to 2mm Pd mounting posts 79 mounted on the top PTFE disk 75.
  • electrolyte 71 consisting of LiOD in D 2 0.
  • Reference electrode 63 is positioned adjacent to cathode 55. All cell 67 surfaces are solvent cleaned and rinsed.
  • the anode cage 73 is further washed with aqua regia and rinsed with D 2 0.
  • the Pd cathode 55 is a 3mm dia. 3 cm long Pd rod, machined from a 1/8" pure Pd wire. Prior to insertion into vessel 69, cathode 55 is solvent cleaned, vacuum annealed at 800°C for two to three hours, and slowly cooled in an atmosphere of Ar. Cathode 55 is finally dipped in heavy aqua regia for 20 seconds and rinsed with D 2 0.
  • the LiOD electrolyte 71 with 200 ppm (molar) Al, is manufactured by adding 0.175g Li metal and approximately 7 mg pure Al foil to 25 ml D 2 0. This procedure is carried out under a nitrogen atmosphere. Electrolyte 71 should be prepared immediately prior to use.
  • An external 180 ohm heater (0.04" dia 72" long) is wound around the outside of vessel 69 within specially machined grooves on the surface 59. These grooves are omitted from the drawing of FIG. 6.
  • Cell 67 is assembled with minimum exposure to air or H 2 0.
  • Approximately 20 ml of 1M LiOD with ⁇ 200 ppm (molar) Al is added to vessel 69.
  • a 1/8" outside diameter Ni tube 81, extending out of cell 67, is attached on the top of vessel 69.
  • Vessel 69 is pressurized to 50 psig with D 2 .

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Méthode de formation d'un film (10) sur la surface d'une cathode (7) pour faciliter la charge d'un isotope hydrogène dans la cathode (7). La cathode (7) et une anode (9) sont immergées dans un électrolyte (5) contenant un isotope hydrogène et des ions conducteurs, tandis que les électrodes sont reliées à une source de courant (11). Les ions conducteurs peuvent être formés par inclusion de LiOH ou de LiOD ou de LiOT dans l'électrolyte (5). L'addition d'autres espèces ou composés élémentaires à l'électrolyte (5) facilite encore la formation du film (10) et renforce la charge de l'isotope hydrogène dans la cathode (7).
PCT/US1993/011754 1992-12-10 1993-12-03 Methodes de formation de films sur des cathodes Ceased WO1994014163A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
US6024935A (en) * 1996-01-26 2000-02-15 Blacklight Power, Inc. Lower-energy hydrogen methods and structures
US7188033B2 (en) 2003-07-21 2007-03-06 Blacklight Power Incorporated Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions
US7689367B2 (en) 2004-05-17 2010-03-30 Blacklight Power, Inc. Method and system of computing and rendering the nature of the excited electronic states of atoms and atomic ions
US7773656B1 (en) 2003-10-24 2010-08-10 Blacklight Power, Inc. Molecular hydrogen laser

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US2534234A (en) * 1948-02-20 1950-12-19 George C Cox Electrocoating method
US4487670A (en) * 1981-12-09 1984-12-11 Commissariat A L'energie Atomique Process for treating solutions containing tritiated water
WO1990010935A1 (fr) * 1989-03-13 1990-09-20 The University Of Utah Procede et appareil de production de puissance
US4986887A (en) * 1989-03-31 1991-01-22 Sankar Das Gupta Process and apparatus for generating high density hydrogen in a matrix

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US1442238A (en) * 1922-07-29 1923-01-16 Smith Albert Kelvin Electrolytic apparatus
US2534234A (en) * 1948-02-20 1950-12-19 George C Cox Electrocoating method
US4487670A (en) * 1981-12-09 1984-12-11 Commissariat A L'energie Atomique Process for treating solutions containing tritiated water
WO1990010935A1 (fr) * 1989-03-13 1990-09-20 The University Of Utah Procede et appareil de production de puissance
US4986887A (en) * 1989-03-31 1991-01-22 Sankar Das Gupta Process and apparatus for generating high density hydrogen in a matrix

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Title
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NATURE, Vol. 342, 23 November 1989, pages 375-384, WILLIAMS et al. *
PHYSICAL REVIEW LETTERS, Vol. 62, No. 25, 19 June 1989, pages 2929-2932, ZIEGLER et al. *
PHYSICIA SCRIPTA, Vol. 40, (September 1989), pages 303-306, SUNDQVIST et al. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6024935A (en) * 1996-01-26 2000-02-15 Blacklight Power, Inc. Lower-energy hydrogen methods and structures
US7188033B2 (en) 2003-07-21 2007-03-06 Blacklight Power Incorporated Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions
US7773656B1 (en) 2003-10-24 2010-08-10 Blacklight Power, Inc. Molecular hydrogen laser
US7689367B2 (en) 2004-05-17 2010-03-30 Blacklight Power, Inc. Method and system of computing and rendering the nature of the excited electronic states of atoms and atomic ions

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