WO1993000684A1 - Appareil produisant de la chaleur a partir d'alliages de palladium deuterise - Google Patents

Appareil produisant de la chaleur a partir d'alliages de palladium deuterise Download PDF

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Publication number
WO1993000684A1
WO1993000684A1 PCT/US1992/004259 US9204259W WO9300684A1 WO 1993000684 A1 WO1993000684 A1 WO 1993000684A1 US 9204259 W US9204259 W US 9204259W WO 9300684 A1 WO9300684 A1 WO 9300684A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
cathode
palladium
boron
deuterium
Prior art date
Application number
PCT/US1992/004259
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English (en)
Inventor
Steven Crouch-Baker
Michael C. H. Mckubre
Stuart I. Smedley
Francis L. Tanzella
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 WO1993000684A1 publication Critical patent/WO1993000684A1/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 alloys of 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. These alloys include palladium-silver, palladium-lithium, palladium-carbon, palladium-lithium-carbon, palladium-beryllium, and palladium-sulphur. Reference is made to the paper by E. Storms and C. Talbott entitled “A Study of Electrolytic Tritium Production", on page 149 of the above-mentioned conference proceedings, summarizing the results obtained from cells using a variety of cathode materials.
  • 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 1_, with both electrodes immersed in an electrolyte 5. in container 3..
  • the current source 1JL drives electric current through the electrolyte 5. from anode 9. to cathode 7..
  • the electrolyte 5 is a solution of lithium deuteroxide and boric acid in heavy water (D2O) .
  • the cathode 7 is comprised primarily of palladium. The current flow through the cell causes the palladium to become loaded with boron and deuterium. It is found that this charging of boron into the cathode 7.
  • the cathode 1_ may include other elements besides palladium, deuterium and boron. Generally the cathode 1 also contains lithium from the LiOD in the electrolyte 5_- Other alloys of palladium such as Pd-Ag may be used as the host material.
  • Pd-Ag alloys of palladium
  • the distinctive feature of boron is that in the palladium crystal lattice it occupies octahedral interstitial sites which might otherwise be occupied by deuterium. This enhances the excess heat production process.
  • a second object of this invention is to provide a device for generating excess heat having an improved efficiency for the production of such excess heat.
  • Another object of this invention is to provide a device for generating excess heat in which the current threshold for excess heat production is substantially decreased.
  • 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 J 2. embodying the invention.
  • Figure 2 is a diagram of the face centered cubic
  • FIG. 3 is a cross sectional front view of an electrolytic cell ⁇ j_ 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 alloy cathode 1_ .
  • This cathode J and an anode 9. are immersed in an electrolyte 5. in container 3..
  • the cathode 1_ and anode _ are coupled to a current generator 1_1 which drives a direct current from the anode 9. to the cathode 7 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 D2O, and also preferably LiOD, typically a 1 molar solution.
  • boric acid, H3BO3 is added to this solution to provide a source of boron for loading into the cathode 1_.
  • This cathode 1_ is preferably fabricated from palladium; however various alloys of palladium may also be used, such as palladium-silver.
  • boron may be preloaded into the cathode 1_, in which case Pd-B is the alloy.
  • the active region of the cathode 1_ is in the vicinity of the surface, the cathode 7.
  • 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. It is desirable to anneal out crystal imperfections and volatilize impurities, and to minimize stresses that may lead to cracks in the palladium surface which will limit the attainable amount of deuterium loading. Oxidation of the surface by O2 or H2O should also be avoided for the same reason.
  • the palladium is annealed in a vacuum furnace at 800°C for three hours and then allowed to cool in 1 atmosphere of D2 gas or argon. After cooling, the Pd surface is etched in deuterated aqua regia, and then rinsed in D 2 0.
  • the solution is formed by allowing pure Li metal or Li2 ⁇ to react with D->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 2 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 ⁇ ) 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.
  • FCC face centered cubic
  • the FCC lattice sites are indicated by the circles having horizontal hatchings. These sites are the locations of the palladium atoms in the crystal.
  • Palladium-silver is a substitutional alloy, in which the silver atoms occupy FCC lattice sites that would otherwise be occupied by palladium atoms.
  • the distinctive feature of deuterium (hydrogen) and boron is that these elements form interstitial alloys in palladium.
  • alloys The palladium-hydrogen system has been extensively studied, and it is known that palladium has a propensity to absorb hydrogen, and that the hydrogen atoms preferably occupy the octahedral interstitial sites in the palladium lattice. These sites lie in the horizontal and vertical planes defined by the lattice sites, and each octahedral site lies midway between two neighboring lattice sites, as indicated in Figure 2 by the open circles .
  • the octahedral sites are not the only available sites for interstitial atoms to occupy.
  • the circles with diagonal hatching define the tetrahedral sites in the lattice.
  • the names of these sites refer to the symmetry of their atomic environment.
  • the "nearest neighbor" palladium atoms i.e. the palladium atoms closest to the site
  • these sites have "octahedral symmetry”.
  • the tetrahedral sites have a lower symmetry than the octahedral sites, and atoms at these sites have a higher energy.
  • the octahedral sites are preferably occupied by the interstitial atoms, but at any finite temperature there is always some occupation of tetrahedral sites as well.
  • hydrogen can be loaded at an atomic ratio of H/Pd greater than unity.
  • the palladium-boron system has also been studied, and reference is made to the article by H. A. Brodowsky and H.-J. Schaller, "Thermodynamics of Nonstoichiometric Interstitial Alloys. I. Boron in Palladium", Transactions of the Metallurgical Society of AIME, Vol. 246, p. 1015 (May 1969) . These authors have analyzed the thermodynamic measurements of the palladium-boron system up to concentrations of 23 percent boron, and determined that the boron atoms also occupy the octahedral interstitial sites in the palladium lattice. Their analysis further indicated that the energy gap between the octahedral sites and the tetrahedral sites is substantially greater for boron than for hydrogen (deuterium) .
  • the increased occupancy of non-octahedral sites by deuterium atoms decreases the average distance between neighboring deuterium atoms in the lattice, according to the diagram in Figure 2.
  • the nearest neighbor octahedral sites are at a distance of 0.28 nanometers apart, while the corresponding nearest neighbor tetrahedral sites are at a distance of 0.19 nm from each other, and the corresponding nearest neighbor octahedral-tetrahedral distance is 0.17 nm.
  • FIG. 3 is a cross sectional front view of an electrolytic cell 61_ embodying the present invention.
  • This cell operates at approximately atmospheric pressure.
  • Vessel j59_ 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 .69..
  • This cathode 5_5_ is a 3 mm diameter 3 cm long rod, machined from 1/8" 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.
  • Anode 65. consists of a 1 meter long, 0.5 mm diameter, Pt wire wound around a cage 73 of five quartz glass rods held in place by two PTFE disks 75. The wire .65. is held in place by attachment to 2 mm Pd mounting posts 7_9 mounted on the top PTFE disk 75.
  • the electrolyte 7JL separates the cathode 5_5_ and anode 65.
  • Reference electrode .63. is adjacent to cathode 55. All surfaces of the cell 62. are solvent cleaned and rinsed.
  • the cell 62. is assembled with minimum exposure to air or moisture.
  • the electrolyte 21 is preferably prepared immediately prior to use and added to the vessel .69. before sealing the cell 61_.
  • tube 8_1 is a 1/8" outside diameter nickel tube.
  • the vessel j59 is preferably pressurized with deuterium.
  • the boron-free electrolyte was a 1.0 M solution of LiOD in heavy water with 200 pp (molar) Al, manufactured by adding 0.175 g of Li metal and approximately 7 mg of pure Al foil to 25 ml D2O. This procedure was carried out under a nitrogen atmosphere.
  • the second experiment was performed using the same apparatus but with boric acid added to the electrolyte 21-
  • the addition of the order of 0.2 millimoles of H3BO3 produced surface regions in the cathode that were loaded with boron to at least 10 atomic percent.
  • This experiment was carried out over a total duration of 1287 hours. Excess heat was first observed after 658 hours of electrolysis and was observed on three separate occasions. The maximum excess power observed was 0.8 watts (300% in excess of the input power) ; the total excess of energy was 0.25 MJ, or 11 MJ/mole of Pd.
  • the addition of boron to the electrolyte 21 coincided with the following effects:
  • the cathode may be fabricated as a palladium-boron alloy before assembly into the cell 12., 62.
  • other palladium alloys such as Pd/Ag, having a similar FCC crystal structure can be used in place of pure palladium for loading with boron and deuterium.
  • the use of boron per se is not intended to be limiting, since other materials that occupy octahedral interstitial sites in the palladium lattice could accomplish the same result.
  • the alloy PdCn ir contains carbon atoms on octahedral interstitial sites, as demonstrated experimentally using powder neutron diffraction [S. B. Siemecki, G. A. Jones, D. G. Swartzfager and R. L. Harlow, Journal of the American Chemical Society, Vol. 107, pp. 4547-4548 (1985)] . Therefore carbon is a good candidate to substitute for boron.

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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 en excédent comporte une source de courant continu (11) reliant une anode (9) et une cathode (7), les deux électrodes (9, 7) étant immergées dans un électrolyte (5). La source de courant (11) fait passer le courant électrique à travers l'électrolyte (5) de l'anode (9) à la cathode (7). L'électrolyte (5) est constitué généralement d'eau lourde contenant une solution de deutéroxyde de lithium et d'acide borique. La cathode (7) est constituée principalement de palladium. Sous l'effet du courant qui passe dans la cuve (12, 67), le palladium se charge de bore et de deutérium, ce qui accroît de façon substantielle l'efficacité de la production de la chaleur excédentaire et abaisse le seuil à partir duquel le courant fournit de la chaleur excédentaire. Dans une autre version de l'invention, la surface de la cathode (7) est constituée d'un alliage de bore et de palladium.
PCT/US1992/004259 1991-06-27 1992-05-20 Appareil produisant de la chaleur a partir d'alliages de palladium deuterise WO1993000684A1 (fr)

Applications Claiming Priority (2)

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US72209491A 1991-06-27 1991-06-27
US722,094 1991-06-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409060A (en) * 1993-09-10 1995-04-25 Weatherford U.S., Inc. Wellbore tool orientation

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1467078A1 (de) * 1962-04-17 1969-01-09 Johnson Matthey Co Ltd Verfahren zum Abtrennen von Wasserstoff aus Wasserstoff enthaltenden Gasgemischen
US4048383A (en) * 1976-02-09 1977-09-13 Battelle Memorial Institute Combination cell
US4132619A (en) * 1976-08-06 1979-01-02 State Of Israel, Ministry Of Industry, Commerce And Tourism, National Physical Laboratory Of Israel Electrocatalyst
US4894302A (en) * 1985-06-14 1990-01-16 The Dow Chemical Company Alkaline earth metal anode-containing cell having electrolyte of organometallic alkaline earth metal salt and organic solvent
JPH02268288A (ja) * 1989-04-10 1990-11-01 Koji Okada 核融合用電解液
WO1990015415A1 (fr) * 1989-06-02 1990-12-13 Johnson Matthey Public Limited Company Ameliorations apportees a des matieres
US4986887A (en) * 1989-03-31 1991-01-22 Sankar Das Gupta Process and apparatus for generating high density hydrogen in a matrix

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1467078A1 (de) * 1962-04-17 1969-01-09 Johnson Matthey Co Ltd Verfahren zum Abtrennen von Wasserstoff aus Wasserstoff enthaltenden Gasgemischen
US4048383A (en) * 1976-02-09 1977-09-13 Battelle Memorial Institute Combination cell
US4132619A (en) * 1976-08-06 1979-01-02 State Of Israel, Ministry Of Industry, Commerce And Tourism, National Physical Laboratory Of Israel Electrocatalyst
US4894302A (en) * 1985-06-14 1990-01-16 The Dow Chemical Company Alkaline earth metal anode-containing cell having electrolyte of organometallic alkaline earth metal salt and organic solvent
US4986887A (en) * 1989-03-31 1991-01-22 Sankar Das Gupta Process and apparatus for generating high density hydrogen in a matrix
JPH02268288A (ja) * 1989-04-10 1990-11-01 Koji Okada 核融合用電解液
WO1990015415A1 (fr) * 1989-06-02 1990-12-13 Johnson Matthey Public Limited Company Ameliorations apportees a des matieres

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ORNL/FTR-3341, 31 July 1989, COOKE, see pages 3-5. *
PHYSICAL REVIEW B, Vol. 42, No. 14, 15 November 1990, pages 9143-9146, (SILVERA et al.). *
THE FIRST ANNUAL CONFERENCE ON COLD FUSION, (Conf. Proceedings), March 1990, Salt Lake City, Utah, pages 149-163, Article by STORMS et al. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409060A (en) * 1993-09-10 1995-04-25 Weatherford U.S., Inc. Wellbore tool orientation

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