USA As Represented by Secretary of the Navy

Millennium Engineering and Integration Company

Other

Melvin H Miles

Aaron N Fletcher

George E McManis, Iii

Dwight A Fine

M Ashraf Imam

John D Stenger-Smith

Andrew P Chafin

William P Norris

Ronald A Henry

Peter Zarras

John W Fischer

Kurt W Solomon

John Nelson

Adam A Grumet

A rechargeable molten salt electrolyte battery has an anode comprising lithium, a cathode electrode comprising a conductive metal that is compatible with the nitrate melt, an electrolyte comprising lithium nitrate or lithium nitrate mixtures with other nitrates which electrolyte is capable of becoming an ionic conductive liquid upon being heated above its melting point, wherein oxygen for reaction at the cathode or within the melt is provided from an external source to be delivered to the cathode through the electrolyte and provision is made to collect lithium oxide formed during discharge to be reconstituted as lithium ions and oxygen during recharge. At least a portion of the oxygen reduction reaction is provided by a nitrate ion pathway.

Rechargeable lithium-air and other lithium-based batteries using molten nitrates

Thermal batteries using molten nitrate electrolytes offer significantly higher cell voltages and improvements in energy and power density. A problem concerning gas-evolution reactions is solved by eliminating chloride ions, sodium ions, and moisture contaminants. One step is to avoid any chlorine-containing substances in any battery component. The decomposition of such substances into chloride ions results in passivating-film breakdown and gas-producing reactions with the electrolyte. Sodium ions also react with the anode and lead to decreased stability. Thus, the use of sodium ions in components of the battery is avoided. The effect of water in the melt relates to both the reactivity and out-gassing problem. Water in the melt will react with, and breach the insoluble and protective oxide film and can produce hydrogen gas. A method to measure water in the nitrate electrolyte melt via cyclic voltammetry, as well as means of eliminate water from the melt is presented.

Chloride-free, sodium ion-free, and water-free thermal batteries using molten nitrate electrolytes

Thermal batteries using molten nitrate electrolytes offer significantly higher cell voltages and marked improvements in energy and power densities over present thermal batteries. However, a major problem is gas-evolution reactions involving the molten nitrate electrolytes. This gassing problem has blocked the advantages offered by thermal batteries using molten nitrates. The solution to this gassing problem is to eliminate the chloride ion contaminates. The most important step in reducing chloride contamination is the avoidance of potassium perchlorate (KClO) or any other chlorine-containing substances that can decompose to produce chloride ions in any thermal battery component. The Fe+KClOpyrotechnic used to activate thermal batteries is a key example. The decomposition of such substances into chloride ions (Cl&#x2014;) results in passivating-film breakdown and gas-producing reactions with the molten nitrate electrolyte. These reactions largely involve the lithium-component of the anode used in thermal batteries such as Li&#x2014;Fe (LAN), Li&#x2014;Si, and Li&#x2014;Al. The introduction of chloride ions into the nitrate melt via the pyrotechnic materials produces a rapid breakdown of the protective oxide film on lithium-based anodes and leads to gas-producing reactions.

Chloride-free thermal batteries using molten nitrate electrolytes

A palladium-boron composition and methods of making and using same are provided. In one aspect, the invention comprises an alloy comprising palladium and boron, the boron being in solid solution in the palladium and the alloy having a two-phase structure, wherein each phase of the two-phase structure has the same crystal structure as the other phase and has a different set of lattice parameters from the other phase such that the palladium is greatly hardened by the presence of the smaller phase crystals within the spaces between the larger phase crystals. The composition is carefully prepared by a process wherein palladium and an amount of boron sufficient to place the boron in solid solution, but insufficient to combine with the palladium, are placed together and repeatedly are melted, cooled and turned over until sufficiently mixed. The hardened composition can be used to create thinner membranes for hydrogen purification and improved electrodes for generation of heat energy, and other electrochemical processes.

Palladium-boron alloys and methods for making and using such alloys

A palladium-boron composition and methods of making and using same are provided. In one aspect, the invention comprises an alloy comprising palladium and boron, the boron being in solid solution in the palladium and the alloy having a two-phase structure, wherein each phase of the two-phase structure has the same crystal structure as the other phase and has a different set of lattice parameters from the other phase such that the palladium is greatly hardened by the presence of the smaller phase crystals within the spaces between the larger phase crystals. The composition is carefully prepared by a process wherein palladium and an amount of boron sufficient to place the boron in solid solution, but insufficient to combine with the palladium, are placed together and repeatedly arc melted, cooled and turned over until sufficiently mixed. The hardened composition can be used to create thinner membranes for hydrogen purification and improved electrodes for generation of heat energy, and other electrochemical processes.

Until recently, conducting polymers have been used as protective coatings. lthough these types of polymers appear to be effective in most cases, problems have resulted when attempting to bind these polymers to an aluminum surface. The polymers of this invention adhere extremely well to aluminum and aluminum alloys and thus, provide a very effective form of corrosion protection.

Amino functional poly (para-phenylene vinylene)s as protective coatings

The addition of cathode materials comprising Cu.sup.++, Fe.sup.+++, Cr.sup.+++ or Au.sup.+++, in the form of salts such as the nitrate or halide, e.g. Fe(NO.sub.3).sub.3 or CuCl.sub.2, to low melting nitrate electrolyte cells increases cell potential. Other ions such as Co.sup.++, Eu.sup.+++, La.sup.+++, Ni.sup.++, Mn.sup.++, Ce.sup.+++, Pr.sup.+++, Nd.sup.+++, Gd.sup.+++, Sm.sup.+++ and Tb.sup.+++, in the form of salts thereof, can also be used, but yield smaller cell potentials. Such cathodic materials in the form of a suitable salt, such as a nitrate or halide, e.g. Fe(NO.sub.3).sub.3 or CuCl.sub.2, are added to low melting fused nitrate electrolytes, e.g. a LiNO.sub.3, KNO.sub.3 mixture, in a concentration sufficient to increase cell potential, using Li or Ca anodes. A suitable metal current collector such as a Ni screen can be used as a cathode. The above cathodic materials can be used in conjunction with other cathodic materials such as AgNO.sub.3, which undergoes reduction to the free metal.

Thermal battery cells containing cathode materials in low-melting

Electrochromic systems providing enhanced cycle lifetime. The increase in cycle lifetime is a product of one or more of the following: novel or known asymmetric viologen compounds, mixed electrolyte systems, and mixed solvent systems.

Enhanced cycle lifetime electrochromic systems

The addition of cathode materials comprising In.sup.+++, Pb.sup.++ or Cd.sup.++ ion, e.g. in the form of salts such as In(NO.sub.3).sub.3, Pb(NO.sub.3).sub.2, Cd(NO.sub.3).sub.2 or the corresponding perchlorates, to oxyanionic electrolyte cells increases cell potential. Such cathodic materials are added to lower melting fused salt oxyanionic electrolytes such as nitrate or perchlorate electrolytes, e.g. LiNO.sub.3, KNO.sub.3 or LiCl0.sub.4, in a concentration sufficient to increase cell potential, using Li or Ca anodes. A suitable metal current collector such as a Ni screen can be used as a cathode. The above cathodic materials can be used in conjunction with other cathodic materials such as AgNO.sub.3, which undergoes reduction to the free metal.

Thermal battery cells containing novel cathode materials in an

A thermal battery cell with a fiberglass wrapping and facial pressure as a eans for wetting the calcium anode to prevent deflagration or flashing using either a homogeneous LiClO.sub.4 and AgNO.sub.3 electrolyte or a non-homogeneous electrolyte arrangement of LiCl, LiNO.sub.3 and AgNO.sub.3.

Thermal cell non-deflagration design

A thermally activated electrochemical cell utilizes a lithium-boron anode and a molten nitrate electrolyte selected from the group consisting of lithium nitrate, a mixture of lithium nitrate and sodium nitrate, a mixture of lithium nitrate and potassium nitrate, and a mixture of lithium nitrate and sodium nitrate with potassium nitrate, to provide improved cell electrical performance. The electrolyte is contained on a fiberglass separator and the electrolyte adjacent to the cathode may contain silver nitrate as well. Current densities over 300 mA/cm.sup.2 with a usable temperature range of over 150.degree. C. have been obtained. Anode open circuit potentials of about 3.2 V were found with little polarization at 100 mA/cm.sup.2 and with very slight polarization at 300 mA/cm.sup.2.

Lithium-boron anodes in nitrate thermal battery cells

A thermally activated electrochemical cell utilizes an anode constructed of lemental lithium and transition metal powder. Iron is disclosed to be the best mode of transition metal powder. The cell uses nitrate salt electrolyte containing lithium nitrate and silver nitrate as a cathode enhancer. Electrical performance of this cell includes open circuit potentials of approximately +3.4 volts at 300.degree. C. and thermal activation within the range of 123.degree. to 465.degree. C. Current densities as high as 1,250 mA/cm.sup.2 have been demonstrated.

High performance molten nitrate cell

A method for the detection of nitrate esters using a solid working electrode of silver, copper, or gold. The method involves the forming of a test solution of a sample and supporting electrolyte, the insertion of the solution into a cell having the solid working electrode, deoxygenation of the test solution, application of a linearly varying potential to the cell and the recording of a voltammogram to show the reduction wave of the nitrate esters.

Detection of nitrate esters using silver electrode

A thermally activated electrochemical cell is provided having a low melting oint electrolyte. The electrolyte is composed of a layer of a mixture of lithium perchlorate and lithium nitrate adjacent the anode and of a layer of a mixture of lithium perchlorate, lithium nitrate, and silver nitrate adjacent the cathode of the cell.

Thermal battery cells utilizing AgNO.sub.3 in LiClO.sub.4 -LiNO.sub.3

A thermal battery cell is provided comprising a low-melting point electroe in the presence of halides, a cathode, an oxidizer and a calcium anode.

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Ridgecrest, CA, United States of America

Melvin H Miles