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WO1993000683A1 - Appareil de production de chaleur a partir de palladium deuterise revetu d'un film - Google Patents

Appareil de production de chaleur a partir de palladium deuterise revetu d'un film Download PDF

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Publication number
WO1993000683A1
WO1993000683A1 PCT/US1992/004241 US9204241W WO9300683A1 WO 1993000683 A1 WO1993000683 A1 WO 1993000683A1 US 9204241 W US9204241 W US 9204241W WO 9300683 A1 WO9300683 A1 WO 9300683A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
recited
cathode
electrolyte
deuterium
Prior art date
Application number
PCT/US1992/004241
Other languages
English (en)
Inventor
Michael C. H. Mckubre
Steven Crouch-Baker
Francis L. Tanzella
Stuart I. Smedley
Joseph Santucci
Romeu C. Rocha-Filho
Original Assignee
Electric Power Research Institute, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Electric Power Research Institute, Inc. filed Critical Electric Power Research Institute, Inc.
Publication of WO1993000683A1 publication Critical patent/WO1993000683A1/fr

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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 pertains generally to the field of devices for producing heat energy by charging palladium with deuterium, and more particularly, to such devices where this charging is carried out by electrochemical means.
  • Cathodes have been fabricated from titanium and a variety of palladium alloys, besides pure palladium. Some researchers have reported deposits of contaminant materials on the cathode during the electrolysis process. These deposits degrade the energy production process by impeding the current flow and interfering with the deuterium loading.
  • the present invention provides an electrolysis system 1 for generating excess heat, having a direct current source 11 coupled between an anode 9. and a cathode 7_, with both electrodes at least partially immersed in an electrolyte 5_ in container 3..
  • the current source 11 drives electric current through the electrolyte 5_.
  • the electrolyte 5_ is preferably a solution of lithium deuteroxide in heavy water (D2O) .
  • the cathode 7. is comprised primarily of palladium, with a surface film designed to enhance the deuterium loading process. This surface film is preferably a hydrated metal oxide-based compound that is permeable to deuterium, and a variety of metals are useful in this film material. The film promotes deuterium loading by inhibiting the formation of
  • D 2 gas bubbles at the cathode surface by blocking the anode material ions in the electrolyte from cathode electrons to prevent the formation of anode material deposits on the cathode, and by coating over cracks and defects in the cathode surface.
  • a second object of this invention is to provide a device for generating excess heat by the electrochemical loading of palladium cathodes with deuterium, in which the formation of deuterium gas bubbles at the cathode surface is inhibited.
  • Another object of this invention is to provide a device for generating excess heat by the electrochemical loading of palladium cathodes with deuterium, in which the formation of anode material deposits on the cathode is prevented.
  • Yet another object of this invention is to provide a device for generating excess heat by the electrochemical loading of palladium cathodes with deuterium, in which a coating is provided over the cathode surface to mitigate the deleterious effects of cracks and defects in the cathode surface.
  • Figure 1 is a schematic diagram of an electrolysis system 1 for generating excess heat according to the present invention, showing a partially cross sectioned elevational view of an electrolytic cell 12. embodying the invention.
  • Figure 2 is a cross sectioned elevational view of the lower portion of the cathode 7_ of Figure 1, showing the film layer 10 over the palladium cathode surface 8. according to the present invention.
  • Figure 3 is a cross sectional front view of an electrolytic cell 67. embodying the present invention.
  • FIG. 1 is a schematic diagram of an electrolysis system 1 for generating excess heat according to the present invention, for loading deuterium into a palladium cathode 7_.
  • This cathode 7. and an anode 9. are at least partially immersed in an electrolyte 5_ in container 3_.
  • the cathode 7. and anode .9. are coupled to a current generator 11 which drives a direct current from the anode 5 . to the cathode 2 within the electrolyte 5_.
  • the entire system may be enclosed in a 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 electrolyte 5_ contains heavy water, specifically D 2 0, and also preferably LiOD, typically a 1 molar solution.
  • the cathode 7_ is preferably fabricated from palladium; however various alloys of palladium may also be used. Since the active region of the cathode 7_ is in the vicinity of the surface, the cathode 7. may actually be a layer of palladium over a bulk region of a conducting metal having a small deuterium diffusivity, such as copper.
  • the anode 9. is preferably fabricated from palladium, platinum, or some stable non-elemental metallic conductor material. The bulk palladium used in practicing the invention should be of high purity.
  • the palladium is annealed in a vacuum furnace at 800°C for three hours and then allowed to cool in 1 atmosphere of D gas or argon. After cooling, the Pd surface is etched in deuterated aqua regia, and then rinsed in D 0.
  • the solution is formed by allowing pure Li metal or Li 0 to react with D 2 0 of high isotopic purity in an inert gas environment.
  • the electrolyte container 3_ should be fabricated from materials that will not form deposits on the surface of the cathode 7. that inhibit the degree of deuterium loading. Two examples of materials that are satisfactory are quartz glass and polytetrafluoroethylene (PTFE) .
  • the cathode 7_ is preferably precharged at a moderate current density (between 10 and 100 mA/cm 2 ) for a time corresponding to several diffusion periods of deuterium in palladium. This time is typically 3 to 10 days. This precharging period facilitates the subsequent accumulation of deuterium in the cathode. The production of excess heat is then initiated by increasing the current density continuously up to a threshold level.
  • the palladium cathode 7. is shown as a layer 8. of palladium over a core 6. of conducting metal that may be impermeable to deuterium, such as copper. Since the deuterium loading takes place only over a limited region near the cathode surface, this inner core 6 . does not play an active role in the heat generation process.
  • the film 10 over the surface of the palladium layer 8. enhances the loading of deuterium into the palladium at the surface covered by the film.
  • This film 10. may be coated on the surface 8 . of the palladium prior to the insertion of the cathode 7 . into the electrolyte 5_.
  • the film 10. may be formed in situ by introducing additive metal species into the electrolyte 5_ and maintaining a moderate current density for a sufficient period to allow the film 10_ to form on the cathode surface 8.
  • the preferred metal species comprise aluminum, silicon, and boron.
  • Other suitable metal species include barium, calcium, copper, iron, lithium, magnesium, nickel, scandium, titanium, vanadium, yttrium, and zirconium.
  • the film 10 may not be of uniform composition or structure. It may comprise, for example, a hydrated oxide-based compound containing the particular metal species introduced into the electrolyte 5_.
  • the compound may be an oxide or a hydroxide of the metal, for example.
  • the film 10_ enhances the deuterium loading process by several mechanisms.
  • the film 10. is permeable to deuterium-transporting ions, and facilitates deuterium transport to the Pd layer 8., while at least partially blocking the transport of impurity cations from the electrolyte 5. and electrons from the palladium 8_ that otherwise could cause the impurity materials to deposit onto the surface 8 . of the cathode 7_.
  • These deposits can inhibit deuterium absorption by forming an impermeable layer, or by catalyzing the alternate competing process of recombination: D ads + D ads ⁇ D 2 (gas) .
  • film 10. hinders recombination by blocking molecular adsorption sites and preventing atomic and molecular diffusion on the surface 8. of the cathode 7..
  • film 10 inhibits the nucleation of D gas bubbles, thereby increasing the effective pressure of deuterium and the limit of loading (D/Pd) .
  • D/Pd limit of loading
  • FIG. 3 is a cross sectional front view of an electrolytic cell .62 embodying the present invention.
  • This cell operates at approximately atmospheric pressure.
  • Vessel .69 is constructed of aluminum and has a cylindrical sleeve shape with an internal surface of PTFE.
  • the palladium cathode 5_5_ is disposed along the central axis of the vessel ⁇ _9.
  • This cathode 5_5_ is a 3 mm diameter 3 cm long rod, machined from 1/8" (typically) pure Pd wire.
  • the cathode 5_5 Prior to insertion, the cathode 5_5 is solvent cleaned, vacuum annealed at 800°C for between 2 and 3 hours, and slowly cooled in an argon atmosphere. Finally it is dipped in heavy aqua regia for 20 seconds and rinsed with heavy water.
  • the electrolysis portion of the cell 67_ is exposed only to materials from the group comprising Pd, Pt, quartz glass and PTFE.
  • Anode .65. consists of a 1 meter long, 0.5 mm diameter, Pt wire wound around a cage 23 of five quartz glass rods held in place by two PTFE disks 75.
  • the wire _6_5_ is held in place by attachment to 2 mm Pd mounting posts 29. mounted on the top PTFE disk 75.
  • the electrolyte 21 separates the cathode 5J5 and anode 65.
  • Reference electrode j53. is adjacent to cathode 55. All surfaces of the cell ⁇ j_ are solvent cleaned and rinsed.
  • the electrolyte 21 is preferably prepared immediately prior to use and added to the vessel .69. before sealing the cell 67_ .
  • tube 81 is a 1/8" outside diameter nickel tube.
  • the vessel j6_9 is preferably pressurized with deuterium.
  • the existence of the film 10. and its electrical characteristics can be determined by measuring the ac impedance between the electrolyte 5. and the cathode 2 as a function of frequency. In the embodiment discussed here, these measurements were made over a frequency range between 0.1 Hz and 10,000 Hz. These data may be analyzed to provide information about the electrochemical kinetic processes of electron transfer, mass transport of product and reactant species, and resistance and reactance of surface films 10_. The information about the characteristics of the film 10. is based on these measurements and analyses.
  • the effect of the film 10 in facilitating heat generation is displayed by varying the amount of aluminum in the electrolyte 5_ and measuring the resistivity of the loaded palladium 8., which gives a measure of the degree of deuterium loading, or the atomic ratio D/Pd.
  • This ratio was measured for the cell with an electrolyte containing no aluminum, and found to be 0.945.
  • the ratio D/Pd increased, up to a value 0.978. This increase corresponds to a change in deuterium fugacity from approximately 10° atmospheres to approximately 2 x 10 8 atmospheres. It was also found that the presence of the film 10 allowed this high loading to be maintained for long periods of time, of the order of weeks or more.

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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

Un système d'électrolyse (1) produisant de la chaleur excédentaire comprend une source de courant continu (11) reliant une anode (9) et une cathode (7). L'électrolyte (5) est généralement constituée d'eau lourde contenant une solution de deutéroxyde de lithium. La cathode (7) présente une couche de surface (8) contenant principalement du palladium. Sous l'effet du passage du courant dans la cuve (12, 67), le palladium se charge en deutérium. La couche de surface (8) est au moins partiellement revêtue d'un film (10) qui améliore le chargement de deutérium dans la couche (8). Le film (10) comprend des composés à base d'oxydes métalliques hydratés, dans lesquels le métal peut être de l'aluminium, du silicium, du bore, du baryum, du calcium, du cuivre, du fer, du lithium, du magnésium, du nickel, du scandium, du titane, du vanadium, de l'yttrium ou du zirconium. Le film (10) est créé à partir d'un matériau contenu dans l'électrolyte (5) soumis au passage du courant. Dans un autre mode de réalisation de l'invention, le film (10) est prédéposé sur la surface de la cathode (7) avant immersion dans l'électrolyte (5).
PCT/US1992/004241 1991-06-27 1992-05-20 Appareil de production de chaleur a partir de palladium deuterise revetu d'un film WO1993000683A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US722,098 1985-04-10
US72209891A 1991-06-27 1991-06-27

Publications (1)

Publication Number Publication Date
WO1993000683A1 true WO1993000683A1 (fr) 1993-01-07

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AU (1) AU2316292A (fr)
WO (1) WO1993000683A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0635844A1 (fr) * 1993-07-20 1995-01-25 James A. Patterson Système pour l'électrolyse de l'eau
WO2007114845A3 (fr) * 2005-12-05 2007-12-21 Irving I Dardik électrodes modifiées pour des générateurs de puissance à réaction nucléaire à basse énergie
US8277418B2 (en) 2009-12-23 2012-10-02 Alcon Research, Ltd. Ophthalmic valved trocar cannula
US8343106B2 (en) 2009-12-23 2013-01-01 Alcon Research, Ltd. Ophthalmic valved trocar vent
US9540960B2 (en) 2012-03-29 2017-01-10 Lenr Cars Sarl Low energy nuclear thermoelectric system
WO2019012120A1 (fr) * 2017-07-13 2019-01-17 Lenr Cars Sa Procédé de production d'énergie à partir d'agrégats condensés d'hydrogène
US10475980B2 (en) 2012-03-29 2019-11-12 Lenr Cars Sa Thermoelectric vehicle system

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113080A (en) * 1961-05-22 1963-12-03 Smith Corp A O Continuous decontamination of the hydrogen acquiring surface of a palladium diaphragm used for the transfer of atomic hydrogen
US3448035A (en) * 1966-01-25 1969-06-03 Milton Roy Co Activated surfaces useful in the production of hydrogen
US3455845A (en) * 1965-03-16 1969-07-15 Varta Ag Method for the production of finely-divided catalyst coatings on pore-free surfaces of hydrogen-absorbing metallic substances,and product resulting therefrom
US3516862A (en) * 1968-04-01 1970-06-23 Gen Electric Rechargeable alkaline-zinc cell with porous matrix containing trapping material to eliminate zinc dendrites
GB1338379A (en) * 1971-04-19 1973-11-21 Int Research & Dev Co Ltd For electrolysis cell water treatment
US3778307A (en) * 1967-02-10 1973-12-11 Chemnor Corp Electrode and coating therefor
US4338167A (en) * 1978-12-27 1982-07-06 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method for increasing electrolytic efficiency of a fusion electrolysis with anodic oxygen generation
US4986887A (en) * 1989-03-31 1991-01-22 Sankar Das Gupta Process and apparatus for generating high density hydrogen in a matrix
WO1991003055A2 (fr) * 1989-08-15 1991-03-07 University Of Utah Methode de preparation d'electrodes utilisables dans un appareil calorifique

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113080A (en) * 1961-05-22 1963-12-03 Smith Corp A O Continuous decontamination of the hydrogen acquiring surface of a palladium diaphragm used for the transfer of atomic hydrogen
US3455845A (en) * 1965-03-16 1969-07-15 Varta Ag Method for the production of finely-divided catalyst coatings on pore-free surfaces of hydrogen-absorbing metallic substances,and product resulting therefrom
US3448035A (en) * 1966-01-25 1969-06-03 Milton Roy Co Activated surfaces useful in the production of hydrogen
US3778307A (en) * 1967-02-10 1973-12-11 Chemnor Corp Electrode and coating therefor
US3516862A (en) * 1968-04-01 1970-06-23 Gen Electric Rechargeable alkaline-zinc cell with porous matrix containing trapping material to eliminate zinc dendrites
GB1338379A (en) * 1971-04-19 1973-11-21 Int Research & Dev Co Ltd For electrolysis cell water treatment
US4338167A (en) * 1978-12-27 1982-07-06 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method for increasing electrolytic efficiency of a fusion electrolysis with anodic oxygen generation
US4986887A (en) * 1989-03-31 1991-01-22 Sankar Das Gupta Process and apparatus for generating high density hydrogen in a matrix
WO1991003055A2 (fr) * 1989-08-15 1991-03-07 University Of Utah Methode de preparation d'electrodes utilisables dans un appareil calorifique

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
FUSION TECHNOLOGY, Vol. 17, July 1990, (SONA et al.), pages 713-717. *
J. OF FUSION ENERGY, Vol. 9, No. 2, June 1990, (ALBAGLI et al.), pages 133-148. *
NATURE, Vol. 342, 23 Nov. 1989, (WILLIAMS et al.), pages 375-384. *
NATURE, Vol. 388, 27 April 1989, pages 737-740, (JONES et al.). *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0635844A1 (fr) * 1993-07-20 1995-01-25 James A. Patterson Système pour l'électrolyse de l'eau
WO2007114845A3 (fr) * 2005-12-05 2007-12-21 Irving I Dardik électrodes modifiées pour des générateurs de puissance à réaction nucléaire à basse énergie
US8277418B2 (en) 2009-12-23 2012-10-02 Alcon Research, Ltd. Ophthalmic valved trocar cannula
US8343106B2 (en) 2009-12-23 2013-01-01 Alcon Research, Ltd. Ophthalmic valved trocar vent
US8679064B2 (en) 2009-12-23 2014-03-25 Alcon Research, Ltd. Ophthalmic valved trocar cannula
US9540960B2 (en) 2012-03-29 2017-01-10 Lenr Cars Sarl Low energy nuclear thermoelectric system
US10475980B2 (en) 2012-03-29 2019-11-12 Lenr Cars Sa Thermoelectric vehicle system
WO2019012120A1 (fr) * 2017-07-13 2019-01-17 Lenr Cars Sa Procédé de production d'énergie à partir d'agrégats condensés d'hydrogène
JP2020527706A (ja) * 2017-07-13 2020-09-10 エルイーエヌアール カーズ ソシエテ アノニムＬｅｎｒ Ｃａｒｓ Ｓａ 高密度の水素クラスターからエネルギーを生成する方法

Also Published As

Publication number Publication date
AU2316292A (en) 1993-01-25

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