HIGH SURFACE AREA METAL NITRIDES OR METAL OXYNITRIDES FOR ELECTRICAL ENERGY STORAGE

Abstract: The present invention concerns a process to produce a high surface area iron nitride, titanium nitride, gamma-molybdenum nitride, niobium oxynitride, tantalum oxynitride, vanadium oxynitride, zirconium oxynitride, titanium oxynitride or molybdenum oxynitride coated substrate for use as an electrical energy storage component in a capacitor or a battery configuration, which process comprises: coating a substrate with a solution or slurry of the corresponding metal halide, converting the metal halide to metal oxide, and converting the metal oxide to metal nitride or oxynitride in a gaseous nitrogen atmosphere at elevated temperature.

Description: HIGH SURFACE AREA METAL NITRIDES OR METAL OXYNITRIDES FOR ELECTRICAL ENERGY STORAGE BACKGROUND OF THE INVENTION Cross Reference to Related Applications This application is a continuation-in-part of U.S. Serial No. 761 ,837 filed December 9, 1 996 and is also a continuation-in-part of U.S. Serial No. 727,821 , filed September 30, 1 996, which is a continuation-in-part of U.S. Serial No. 21 9,965, filed March 30, 1 994, which claims priority on U.S. Philippine Serial No. 93/5773, filed September 20, 1 993 and which is also a continuation-in-part of U.S. Serial No. 947,41 4, filed September 1 8, 1 992, now U.S. Patent 5,384,685, U.S. Serial No. 947,294, filed September 1 8, 1 992, now U.S. Patent 5,464,453, and U.S. Serial No. 958,506, filed October 7, 1 992, now abandoned. It is also a continuation-in-part of and claims priority on PCT/US95/03985, filed March 30, 1 995, which claims priority on U.S. Ser. No. 21 9,965, filed March 30, 1 994 and U.S. Ser. No. 377, 1 21 , filed January 23, 1 995. All of these prior issued patents and patent applications are herein incorporated by reference in their entirety. Field of the Invention The present invention concerns a process for the formation of a thin film of a porous metal nitride or metal oxynitride having a high surface area on the surface of an electrically conducting substrate. The metal chloride is dissolved in a volatile organic liquid, a substrate is coated with a film, the film is converted to the porous metal oxide which is then converted to the porous metal nitride or metal oxynitride. The thin layer metal oxynitride covered-substrate is useful for electrical energy storage as an electrode in a capacitor or battery configuration. The present invention generally relates to an energy storage device, and more particularly to a bipolar double layer capacitor-type energy storage device, and to improved methods for manufacturing the same. Description of the Related Art Energy Storage Devices --There has been significant research over the years, relating to useful reliable electrical storage devices, such as a capacitor or a battery. Large energy storage capabilities are common for batteries; however, batteries also display low power densities. In contrast, electrolytic capacitors possess very high power densities and a limited energy density. Further, carbon based electrode double-layer capacitors have a large energy density; but, due to their high equivalent series resistance (ESR), have low power capabilities. It would therefore be highly desirable to have an electrical storage device that has both a high energy density and a high power density. Ultracapacitors provide one approach to meet the high power requirements for the advanced energy storage system for many uses, from cardiac pacemakers to cellular phones to the electric automobile. Until recently, the only packaged high power ultracapacitor material available for significant charge storage has been a mixed ruthenium and tantalum oxide (Z.W. Sun and K.C.Tsai, J. Electrochem. Soc. Ext. Abs., vol. 95-2, pp. 73-76 ( 1 995) and R. Tong et al., United States Patent, 5,464,453 ( 1 995)). Unfortunately, ruthenium and tantalum oxide are expensive. It would be useful to have a reliable long-term electrical storage device, and improved methods to produce the same. It would also be desirable to have an improved energy storage device with energy densities of at least 20-90 J/cc. Additional references of interest include, for example: V. Hock, et al. US Patent No. 5,055, 1 69 issued October 8, 1 991 ; H. Beer US Patent no. 4,052,271 issued October 4, 1 977; and A. Martinsons, et al. US Patent no. 3,562,008 issued February 9, 1 971 . J. Wilfred in US Patent No. 4,774, 1 93, issued September 27, 1 988; and Maruyama et al in US Patent No. 4,764, 1 81 issued August 1 6, 1 988. A number of reports are found in the art to produce various metal nitrides having high surface area. Metal nitrides of particular interest include molybdenum nitride, titanium nitride or iron nitride. Some additional specific references in this art include the following: PCT/US93/08803, filed 1 7 September 1 993, Inventors: Tsai, K.C. et al., Int. Pub. No.: WO 94/07272, Int. Pub. Date: 31 Mar 1 994. PCT/US95/03985, filed 30 March 1 995, Inventors: Tsai, K.C. et al., Int. Pub. No.: WO 95/26833, Int. Pub. Date: 1 2 Oct 1 995. PCT/US95/1 5994, filed 1 1 December 1 995; Inventors: L.T. Thompson et al., Int. Pub. No. WO 96/1 9003, Int. Pub. Date: 20 June 1 996. Robert R. Tong, et al., U.S. Patent No.: 5,464,453, Issued: Nov. 7, 1 995. Robert Tong et al., U.S. Patent No.: 5,384,685, Issued: Jan. 24, 1 995. Additional U.S. Patents of general interest include 4,51 5,763; 4,851 ,206; 5,062,025; 5,079,674; 4,327,400; and 5, 1 85,679. Molybdenum Nitride (Mo 2 N, MoN) -- Low cost, high surface area, and conductive molybdenum nitride is a potential candidate as an alternative material for a high charge storage capacitor. Many reports appear in the literature which describe the formation of molybdenum nitride as a powder having high surface area. A number are listed below. However, none of these references disclose the formation of an adherent film of high surface area molybdenum nitride having improved adhesion on a substrate on a surface. The reaction of powdered molybdenum oxide (Mo0 3 ) with ammonia (NH 3 ) is described to produce ^-molybdenum nitride (Mo 2 N), which has a fee structure with a surface area in excess 200 m 2 /g (L. Volpe and M. Boudart, J. Solid State Chem., 59, 332 ( 1 985)). For molybdenum nitride production and testing, the following art is of interest: D. Finello in "New Developments in Ultracapacitor Technology" reported at the Fourth International Seminar on Double Layer Capacitors and Similar Energy Storage Devices (Volume 4) December 1 2-14, 1 994, Deerfield Beach, Florida reported a study of a molybdenum nitride sample. The molybdenum nitride was described as being prepared by treatment of the oxide film on the surface of a solid foil with ammonia at elevated temperatures. The results show that the nitride is marginally useful as a porous energy storage. D. Finello in "Characterization of Molybdenum Nitride Electrodes" reported at the Fifth International Seminar on Double Layer Capacitors and Similar Energy Storage Devices, December 4-6, 1 995, Boca Raton, Florida describes the comparison of molybdenum nitrides formed by heating the molybdenum oxide film on the surface of a substrate with ammonia. MoCI 5 may be used as a starting material. The product Mo 2 N is not pure and is contaminated with Mo0 2 and MoN. M. Wixom in "Non-Oxide Ceramic Electrodes", disclosed at the Fifth International Seminar on Double Layer Capacitors and Similar Energy Storage Devices, December 4-6, 1 995, Boca Raton, Florida, Vol. 5 that certain metal nitride and metal carbide electrodes can be used for volumetric energy density and power density. Additional detail is not provided. M. Goodwin in "PRI Ultracapacitors and Evaluation of Molybdenum Nitride" reported at the Fifth International Symposium on Double Layer Capacitors and Similar Energy Storage Devices, December 4-6, 1 995, Boca Raton, Florida, in general that molybdenum nitride may make a useful electrode. The specific production of such an electrode was not disclosed or enabled. L. Volpe and Boudart M. "Compounds of molybdenum and tungsten with high specific surface area". Journal of Solid State Chemistry, vol.59, 332-347 (1 985). L. Volpe and Boudart M. "Ammonia synthesis on molybdenum nitride". J. Phys. Chem. vol.90, 4874-4877 ( 1 986). G.S. Ranhotra, et al., "Catalysis over molybdenum carbides and nitrides II. Studies of CO hydrogenation and C 2 H 6 hydrogenolysis" . Journal of Catalysis, vol. 1 08, 40-49 ( 1 987). G.S. Ranhotra, et al., "Catalysis over molybdenum carbides and nitrides I. Catalyst characterization" . Journal of Catalysis, vol. 108, 24-39 (1987). E.J. Markel and Van Zee, J.W. "Catalytic hydrodesulfuriza-tion by molybdenum nitride". Journal of Catalysis, vol. 1 26, 643-657 (1 990). CH. Jaggers, Michaels, J.N. and Stacey, A.M. "Preparation of high-surface area transition-metal nitrides: Mo 2 N and MoN. Chemistry of Materials, vol. 2, 1 50- 1 57 ( 1 990) . J-G. Choi, Choi, D. and Thompson, L.T. "Preparation of molybdenum nitride thin films by N + ion implantation". J. Mater. Res. vol. 7, 374-378 (1 992). L.T. Thompson, Colling, C.W., Choi, D., Demczyk, B.G. and Choi, J-G. "Surface and catalytic properties of molybdenum nitrides". New Frontiers in Catalysis. 1 9-24 ( 1 992). Jeong-Gil Choi. "Temperature-programmed desorption of H 2 from molybdenum nitride thin films". Applied Surface Science, vol. 78, 299-307 (1 994). R.S. Wise, and Markel, E.J. "Catalytic NH3-decomposition by topotactic molybdenum oxides and nitrides: Effect on temperature programmed -M0 2 N Synthesis" . Journal of Catalysis, vol. 145, 335-343 ( 1 994). K.L. Roberts and Markel, E.J. "Generation of M0 2 N nanoparticles from topotactic M02N Crystallites". J. Phys. Chem. vol. 98, 4083-4086 (1 994). R.S. Wise and Markel, E.J. "Synthesis of high surface area molybdenum nitride in mixtures of nitrogen and hydrogen" . Journal of Catalysis, vol. 145, 344- 355 ( 1 994). J-G. Choi, Curl, R.L. and Thompson, L.T. "Molybdenum nitride catalysts" . Journal of Catalysis, vol. 1 46, 21 8-227 ( 1 994). B.G. Demczyk, Choi, J-G and Thompson, L.T. "Surface structure and composition of high-surface-area molybdenum nitrides". Applied Surface Science. vol. 78, 63-69 (1 994). E.P. Donovan and Hubler, G.K. "lon-beam-assisted deposition of molybdenum nitride films. " Surface and Coatings Technology, vol. 66, 499-504 ( 1 994). C.W. Colling and Thompson, L.T. "The structure and function of supported molybdenum nitride hydrodenitrogenation catalysts". Journal of Catalysis, vol. 1 46, 1 93-203 ( 1 994). CH. Jaggers. "The preparation and characterization of high surface area transition metal nitrides" . U.M.I. Dissertation Services. ( 1 994). M.S. Mudholkar and Thompson L.T. "Control of composition and structure for molybdenum nitride films synthesized using ion beam assisted deposition". J. Appl. Phys. vol. 77, 51 38-5143 (1 995). H. Joon Lee, Choi, J-G, Colling, C.W., Mudholkar, M.S. and Thompson, L.T. "Temperature-programmed desorption and decomposition of NH 3 over molybdenum nitride films" . Applied Surface Science, vol. 89, 1 21 -1 30 ( 1 995). Titanium Nitride (TiN) ~ Titanium nitride has a number of uses in the art. It is used to strengthen surfaces as a coating, as semiconductor layer and as electrode materials in electrical applications. Some references of interest concerning titanium nitride include: S.R. Kurts and Gordon, R.G. "Chemical vapor deposition of titanium nitride at low temperatures" . Thin Solid Films, vol. 1 40, 277-290 ( 1 986). P. Mehta, Singh, A.K. and Kingon, A.I. "Nonthermal microwave plasma synthesis of crystalline titanium oxide & titanium nitride nanoparticles" . Mat. Res. Soc. Symp. Proc. vol. 249, 1 53-1 58 ( 1 992). E.O. Travis and Fiordalice, R.W. "Manufacturing aspects of low pressure chemical-vapor-deposited TiN barrier layers" . Thin Solid Films, vol. 236, 325-329 ( 1 993). Y.W. Bae, Lee, W.Y., Besmann, T.M., Blau, P.J. and Riester, L. "Synthesis and selected micro-mechanical properties of titanium nitride thin films by the pyrolysis of tetrakis titanium in ammonia" . Mat. Res. Soc. Symp. Proc. vol. 363, 245-250 ( 1 995). H. Rode, and Hlavacek, V. "Detailed kinetics of titanium nitride synthesis" . A/chE Journal, vol. 41 , 377-388 ( 1 995). K-T. Rie, Gebauer, A., Wohie, J., Tonshoff, H.K. and Blawit, C. "Synthesis of TiN/TiCN/TiC layer systems on steel and cermet substrates by PACVD". Surface and Coating Technology, vol. 74-75, 375-381 ( 1 995). J.N. Musher, and Gordon, R.G. "Atmospheric pressure chemical vapor deposition of titanium nitride from tetrakis (diethylamido) titanium and ammonia". J. Electrochem. Soc. 143, 736-744 (1 996). In these applications, titanium oxide is used to produce the titanium nitride. The surface area is usually low and the electrical storage capacities are marginal. Iron Nitride (FeN) ~ Iron nitride is described in few references. For iron nitride production, the following art is of general interest: A. Tasaki, Tagawa, K., Kita, E., Harada, S. and Kusunose, T. "Recording tapes using iron nitride fine powder" . IEEE Transactions on Magnetics, vol. MAG-1 7, 3026-3031 ( 1 981 ). K. Tagawa, Kita E. and Tasaki, A. "Synthesis of fine Fe 4 N powder and its magnetic characteristics", vol. 21 , 1 596-1 598 ( 1 982). M. Kopcewicz, Jagielski, J., Gawlik, G. and Grabias, A. "Role of alloying elements in the stability of nitrides in nitrogen-implanted σ-Fe" . J. Appl. Phys. vol. 78, 1 31 2-1 321 ( 1 995). D.C Sun, Lin, C, Jiang, E.Y. and Wu, S.W. "Multiphase iron nitride gradient films" . Thin Solid Films, vol. 260, 1 -3 ( 1 995). K.H. Jack. "The synthesis and characterization of bulk σ"-Fe 16 N 2 " . Journal of Alloys and Compounds, vol. 222, 1 60-1 66 ( 1 995). T. Chuijo, Hiroe, K., Matsumura, Y., Uchida, H. and Uchida, H.H. "Reactivity of N 2 with Fe in FeN x formation by activated reactive evaporation process" . Journal of Alloys and Compounds, vol. 222, 1 93-1 96 ( 1 995). F. Maiengreau, Hautier, V., Vermeersch, M., Sporken, R. and Caudano, R. "Chemical interactions at the interface between aluminum nitride and iron oxide determined by XPS" . Surface Science, vol. 330, 75-85 ( 1 995). None of these is art or in any configuration teaches or suggests the present invention. Additional references of general interest include U.S. Patents 3,71 8,551 ; 4,81 6,356; 4,052,271 ; 5,055, 1 69; 5,062,025; 5,085,955; 5, 141 ,828; and 5,268,006. The metal oxynitrides have been studied, usually for use as a dense coating to provide chemical and physical resistance to surfaces. Titanium nitride (TiN) has been studied extensively because of its many useful applications. It is already used as a wear-resistant coating on tools, as a gold substitute for decorative coatings and for thin film resistors. Its metallic conductivity and refractory stability make it the material of choice for diffusion barrier in microelectronics applications. S. Kurtz et al. in Thin Solid Films vol. 140, p. 277 ( 1 986) measured 3μm TiN film that had 8.5 Moh's hardness scale, on which diamond is 10. It has the resistivity of 55 μΩ cm. Most of TiN thin films are produced by chemical vapor deposition (see, for example J.N. Musher et al. J. Electrochem Soc, vol. 1 43, p. 277 (1 996), E.O. Travis, et al., Thin Solid Films, vol. 236, p. 325 (1 993) and K.-T. Rie, et al., Surface and Coating Tech.. vol. 74-75, p. 375 (1 995)): 2TiCI 4 + N 2 + H 2 →2TiN + 8HCI 900-1 200 °C 6TiCI 4 + 8NH 3 →6TiN + 24HCI + N 2 500°C Titanium Oxynitride (TiNO) is a stable intermediate chemical product between titanium oxide and titanium nitride. These thin films of TiNO formed by sputtering are used as an anti-reflection coating (T.R. Pampalone, et al., J. Electrochem Soc, vol. 1 36, p. 1 1 81 ( 1 989)) and/or a diffusion barrier (N. Kumar, et al. Thin Solid Films, vol. 1 53, p. 287 ( 1 987)). Only gas nitriding of titanium dioxide (Ti0 2 ) produces high surface area titanium oxynitride ((CH. Shin, et al.. Journal Solid State Chemistry, vol. 95, p. 1 45 ( 1 991 )). H. Teraoka, et al., in Japanese Patent 89 - 60729 describe that the titanium oxynitride is obtained by the reduction of Ti0 2 in nitrogen atmosphere. Additional references for TiNO include: CH. Shin, et al.. Journal of Solid State Chemistry, vol. 95, 145-1 55 ( 1 991 ) disclose the preparation and characterization of titanium oxynitride having high specific surface area. R. Marchand, et al., U.S. Patent 4,964,01 6 disclose multi-layer ceramic capacitors having as the conductive elements therein, layers of perovskites containing oxygen and oxygen. However, these perovskite metal ( 1 ) metal (2) oxygen nitrogen structure compounds still have low conductivity. No capacitance data has been disclosed. K. Kamiya, et al. in the Journal of Materials Sciences, vol. 22, p. 937-941 (1 987) disclose the nitridation of Ti0 2 fibers prepared by the sol-gel method. All of the applications, patents, articles, references, standards, etc. cited in this application are incorporated herein by reference in their entirety. The present invention provides a process to produce a lower cost, adhering layer of porous high surface area metal nitride or metal oxynitride on a metal sheet (foil) substrate, and a neutral aqueous electrolyte. SUMMARY OF THE INVENTION The present invention concerns a high specific surface area electrode comprising a substrate of an electrically conducting metal or an alloy, and a film layer thereon one or both flat surfaces wherein the film comprises a high surface area nitride or an oxynitride of the metals of Groups III, IV, VI, VI or VII of the Periodic Table. The present invention concerns a process to produce a high surface area iron nitride, titanium nitride or gamma-molybdenum nitride coated substrate for use as an electrical energy storage component in a capacitor or a battery configuration, which process comprises: (a) coating one or both flat etched surfaces of a solid substrate, which substrate is in the form of a thin sheet, with a slurry or solution of a metal halide selected from iron halide, titanium halide or molybdenum halide and a liquid volatile carrier to produce a thin surface film; (b) contacting the metal halide surface film-carrier coated substrate of step (a) with oxygen, air, or combinations thereof at a temperature of between about 1 50 and 400° C for between about 5 and 60 min to convert the iron halide, titanium halide or molybdenum halide to oxide, respectively, as a thin film and to remove the liquid volatile carrier; (c) repeating steps (a) and (b) as needed to obtain an accumulated thickness of metal oxide coating on the substrate, which accumulated metal oxide coating has a high surface area and the volatile carrier is removed; (d) heating the metal oxide film coated substrate of step (c) in oxygen, air or combination thereof at between about 1 50 and 400°C for between about 1 and 3 hr to convert at least about 95% of the metal chloride to metal oxide; (e) slowly increasing the temperature of the metal oxide coated substrate at a rate of less than about 40°C per minute in a nitrogen atmosphere to between about 500 to 800°C; (f) contacting the oxide coated substrate produced in step (d) with a nitrogen source selected from excess flowing gaseous ammonia or a mixture of hydrogen gas and nitrogen gas at between about 500 and 800°C for between 1 and 6 hr which treatment converts about 95 % or greater of the oxide coating to an iron nitride, titanium nitride or gamma-molybdenum nitride layer, respectively, on the substrate, which nitride layer has a high surface area and is electrically conductive; and (g) cooling to ambient temperature and recovering the high surface area nitride coated substrate produced in step (e). In one embodiment, in step (a) the metal chloride is molybdenum chloride, and the gamma-molybdenum nitride film of step (f) has a surface area in excess of 1 6 m 2 /g. In another embodiment, in step (g) the metal nitride formed on the substrate has a surface area of between about 10 and 60 m 2 /g, and a specific capacitance up to about 1 30 F/g. The present invention also concerns a process to produce a high surface area niobium oxynitride, tantalum oxynitride, vanadium oxynitride, zirconium oxynitride, titanium oxynitride or molybdenum oxynitride coated substrate for use as an electrical energy storage component in a capacitor or a battery configuration, which process comprises: (a) coating one or both flat etched surfaces of a solid substrate, which substrate is in the form of a thin sheet, with a solution or a slurry of a metal halide selected from niobium halide, tantalum halide, vanadium halide, zirconium halide, titanium halide or molybdenum halide and a liquid volatile carrier to produce a thin surface film; (b) contacting the metal halide surface film-carrier coated substrate of step (a) with oxygen, air, or combinations thereof at a temperature of between about 1 50 and 250° C for between about 5 and 60 min to convert the metal halide to metal oxide, respectively, as a thin film and to remove the liquid volatile carrier; (c) repeating steps (a) and (b) as needed to obtain an accumulated thickness of metal oxide coating on the substrate, which accumulated metal oxide coating has a high surface area and the liquid volatile carrier is removed; (d) heating the metal oxide film coated substrate of step (c) in oxygen, air or combination thereof at between about 1 50 and 400°C for between about 1 and 3 hr to convert at least about 95 % of the metal chloride to metal oxide; (e) slowly increasing the temperature of the metal oxide coated substrate at a rate of less than about 40°C per minute in a nitrogen atmosphere to between about 500 to 800°C; (f) contacting the oxide coated substrate produced in step (e) with a nitrogen source selected from excess flowing gaseous ammonia, a mixture of ammonia gas and hydrogen gas, or a mixture of hydrogen gas and nitrogen gas at between about 500 and 800°C for between 1 and 6 hr which treatment converts about 95 % or greater of the oxide coating to an niobium oxynitride, tantalum oxynitride, vanadium oxynitride, zirconium oxynitride, titanium oxynitride or molybdenum oxynitride layer, respectively, on the substrate, which oxynitride layer has a high surface area and is electrically conductive; and (g) cooling to ambient temperature and recovering the high surface area metal oxynitride coated substrate produced in step (f). In a preferred embodiment, the metal of the metal oxynitride is selected from molybdenum, niobium, tantalum, titanium, vanadium or zirconium, more preferably titanium or molybdenum. The present invention also relates to a double layer battery or capacitor device, which device comprises at least one cell having: (a) a high surface area adherent coating of a metal oxide, metal carbide, metal nitride, metal oxynitride or combinations thereof coated on an electrically conducting support (b) an opposing high surface area adherent coating of a metal oxide metal carbide, metal nitride, metal oxynitride or combinations thereof coated on an electrically conducting support; and (c) within the volume created between (a) and (b) a substantially neutral aqueous solution of an alkali metal halide. In one embodiment the double layer battery or capacitor device of Claim 1 in (a) and (b), the coating is selected rom the group consisting of a metal nitride, a metal oxynitride or combinations thereof. In one embodiment the alkali metal halide is selected from the group consisting of NaCI, KCI, NaBr, and KBr. In one embodiment the alkali metal halide is present in between 0.5 and 4.5M. In one embodiment in (a) and (b), the coating is selecting from nitride, metal oxynitride, or combinations thereof, in (c) the alkali metal halide is KCI present in between about 1 .0 and 4.0M. In one embodiment in (a) and (b), the metal is selected from iron, titanium, molybdenum, niobium, tantalum, vanadium, zirconium or combinations thereof. The metal nitride electrode or oxynitride electrode (e.g., TiNO) in the presence of a neutral alkaline earth halide aqueous electrolyte produces a stable cell which can be charged and recharged up to 1 .6V. The present invention also relates to a novel electrical storage device that has a high energy density, high power density, and long useful life time. It is an object of the present invention to provide new methods for manufacturing the storage device. It is also another object of the present invention to provide a reliable long-term electrical storage device, and improved methods to produce the same. It is a further object of the present invention to provide efficient packaging of an electrical storage device by reducing the gap between the anode and cathode, which reduces the electrical resistance of the ionically conducting electrolyte. BRIEF DESCRIPTION OF THE FIGURES The above and other features of the present invention and the manner of attaining them, will become apparent, and the invention itself will be best understood, by reference to the following description and the accompanying drawings, wherein: Figure 1 is a schematic representation of an exploded view of the preunit illustrating three cells and is equivalent to Figure 3 in U.S. Patent 5,384,685. Figure 2 is a spectral representation of an x-ray diffraction pattern of Mo 2 N film. Figure 3 is a graphic representation of cyclic voltammetry of Mo 2 N film in 1 molar potassium hydroxide and 3.5 molar sulfuric acid. Figure 4 is a graphic representation of the cyclic voltammetry of TiNO in 3.5M sulfuric acid and in 1 M potassium hydroxide. Figures 5A to 5F show scanning electron micrographs of three different TiNO samples. Figures 5A, 5B and 5C are each at 200 magnification. Figures 5D, 5E and 5F are each at 1000 magnification. Figure 6 is a graphic representation of the capacitance in F/cm 2 and specific capacitance in versus BET specific surface area in m 2 /g for TiNO in 1 M potassium hydroxide. Figure 7A is a spectrographic representation of the XRD data for TiNO for a fresh sample; Figure 7B is after 1 20 CV cycles ( 1 6 hrs) in 1 molar KOH, and Figure 7C is after 1 20 hrs CV cycles ( 1 6 hrs) in 3.5M sulfuric acid. Figures 8A, 8B and 8C are scanning electron micrographs at 1 000 magnification of the titanium oxynitride as a fresh sample, after 1 20 CV cycle in 1 M KOH and after 1 20 CV cycles in 3.5M sulfuric acid, respectively. Figures 9A and 9B show scanning electron micrographs at 20 magnification for TiNO and 100 magnification for RuTaO x , respectively. Figures 10A, 10B and 1 0C show scanning electron micrographs at 200 magnification of TiNO with 0%Mn, 5 % Mn and 1 0% Mn, respectively. Figure 1 1 is a graphic representation of ESR for real impedance versus frequency in herz for TiNO in 1 M potassium hydroxide and for RuTaOx in 4.6 M sulfuric acid. Figure 1 2 is a graphic representation for the leakage current test in 1 M potassium hydroxide for TiNO for leakage current density in //A/cm 2 versus time in hours. Figures 1 3A, 1 3B and 1 3C are scanning electron micrographs of TiNO for a fresh sample ( 1 3A) and after EDM cut, wash and dry ( 1 3B and 1 3C), respectively. Figures 14A and 14B are scanning electron micrographs at 1000 magnification of TiNO and TiNO plus Ti0 2 , respectively. Figure 1 5 is a graphic representation of a Ragone plot of TiNO single cell device of energy density of Wh/kg versus power density in watts/kg. Figure 1 6 is a graphic representation of the TiNO stability test of capacitance in F/cm 2 versus cycles for CV materials, single cell device and for a five cell device. Figures 1 7A and 17B are scanning electronic micrographs at 250 magnification showing crack structure of TiNO and RuTaOx, respectively. Figure 1 8 is a graphic representation of an aqueous 1 .0 M LiCI single cell clamped test sample showing plots for test before and after leaking current test and wherein the sample is submerged within and also is removed from the electrolyte. Real impedance (in ohms) versus frequency (Hz) is shown. Capacitance in (F) is also plotted. Figure 1 9 is a graphic representation of an aqueous 1 .OM LiCI single cell clamped test sample showing the same variables as described in Figure 1 8. Figure 20 is a graphic representation of a single cell test sample in aqueous 1 .OM LiCI and in 1 .0 M KOH for an 1 8 hr test which plots leakage current (in mA) versus time (in hr.). Figure 21 is a graphic representation of a single cell devices for performance degradation of discharge capacitance which plots capacitance (in Farads) versus various types of electrolytes over discharge cycles 500-5000, 1 .OM KCI, 1 .OM KCI (with a glass separator, and 1 .OM CsCI. Figure 22 is a graphic representation of a single cell device for performance degration of discharge energy. The discharge energy in Joules is plotted versus cycles (500-5000). The electrolytes are aqueous solutions of 1 .OM LiCI 1 .OM KOH, 6.0M KOH, 1 .0M KCI, 1 .OM KCI (with a glass separator) and 1 .OM CsCI. Figure 23 is a graphic representation of TiNO x electrodes AC impedance data which plots real impedance (in ohms) versus frequency (Hz). Capacitance in Farads is also plotted. The aqueous solutions include 1 .OM KOH, 6.0M KOH, 1 .OM KCI (cap), 1 .OM KCI gls, 1 .OM LiCI; 1 .OM CsCI, 1 .OM, CsCI (real), 1 .OM KCI (real), 1 .OM KCI gls (real) 1 .OM KCI (real), 6.0M KOH (real), and 1 .OM (real). Figure 24 is a graphic representation of TiNO electrodes for an 1 8 hour leakage current test for a single cell device clamped sample in various electrolytes leakage current (μA) is plotted versus time (hr). Figure 25 is a bar graph comparative representation for a single cell device for ESR (beginning) and ESR (end) at 1000 Hz (in ohms) for various electrolytes. Figure 26 is a bar graph comparative representation for a single cell sample for capacitance (charged) and capacitance (discharged) for various electrolytes. Figure 27 is a bar graph representation which compares the energy of a single cell samples for a charged electrode and for a discharged electrode using various electrolyte compositions and concentrations. Figure 28 is a bar graph representation which compares the charge efficiency and energy efficiency of a single cell sample for various electrolyte compositions and concentrations. Figure 29 is a graphic representation of two TiNO devices tested as single cells, which plot ESR (in ohms) versus F (Hz). Figure 30 is a graphic representation of a TiNO device tested as 5-cells which plots ESR (in ohms) versus Frequency (Hz). Capacitance (Farad) is also plotted. Figure 31 is a graphic representation of three cell devices of TiNO which plots leakage current (μ A/cm 2 ) versus time in minutes. Figure 32 is a graphic representation of a TiNO material which plots current (mA) versus voltage (V v. SHE). Figure 33 is a graphic representation of a 5-cell TiNO device in 1 .OM KCI at various charging voltages, which plots charge (m A Hour) versus cycles (0 to 1 000). Figure 34 is a graphic representation of a 5-cell TiNO device in 1 .OM KCI at various charging voltages which plots Energy (mWHs) versus cycles (0 to 1000). Figure 35 is a graphic representation of the test of various 5-cell devices which plots real impedance (ohm) versus frequency (Hz). Capacitance in Farads is also plotted. Figure 36 is a graphic representation of the test of three 5-cell devices which plots current density (μA/cm 2 ) versus time (hr). Figure 37 is a graphic representation of the cycle test of various 5-cell devices which plots discharge energy (Joules) versus cycles (0 to 5000). Discharge capacitance in Farads is also listed. Figure 38 is a graphic representation of two devices using 1 .0 KCI which plots real impedance (in ohms) versus frequency (Hz). Capacitance in Farads is also recorded. Figure 39 is a graphic representation of a test of two TiNO devices using a single and double gasket with 1 .OM KCI at 1 0.0V plotting leakage current in μA versus time in minutes. Figure 40 is a graphic representation of the freezing point (°C) versus molarity (M) for KCI in aqueous solution. Conductivity in siemans is also plotted versus molarity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Definitions As used herein: The definitions and text of U.S. Patent 5,464,453, WO94/07272 and W095/26833 are incorporated herein in their entirety. The definitions of the following terms are not intended to be exclusive: "Electrically conducting support material" refers to any electrically conducting metal or metal alloy, electrically conducting polymer, electrically conducting ceramic, electrically conducting glass, or combinations thereof. Metals and metal alloys are preferred for producing stock units. Preferred metals include, for example, the metals of the following preferred metal oxides listed for the following second electrically conducting materials. The support material should have a conductivity of greater than about 10 "4 S/cm. "Etched" or "Pretreated" substrate refers to a metal foil or sheet which has been cleaned as described in U.S. Patent 5,464,453, or by contact with a 6N HCI solution for 1 0-1 5 minutes or polished using mechanical polishing. "Halide" refers to the starting material metal chloride, bromide or combinations thereof. Chloride is preferred. "Liquid volatile carrier" refers to any organic liquid which has a boiling point at ambient pressure of about 200°C or below. Usually, only combinations of carbon, hydrogen, oxygen and nitrogen are present. Suitable carriers include, but are not limited to ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, diethyl ether, dioxane, tetrahydrofuran, dimethylacetamide, diethylacetamide, acetone, methylethyl ketone, butanone, ethyl acetate, propyl acetate, methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, xylene, and mixtures thereof. Preferably, the alcohols are used, more preferably, ethanol and propanol. "Second electrically conducting material" (having a high surface area) refers to a porous electrode coating which may be of the same or different composition on each side of the support material. Preferred metal oxides of the present invention include those independently selected from tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, manganese, lanthanum, or lanthanum series metals or alloys or combinations thereof, and possibly containing additives like calcium to increase electrical conductivity. "Electrolyte" refers to an ionically conductive aqueous or non-aqueous solution or material, which enables the dry preunit to be electrically charged. "Cab-0-Sil ® " refers to silica filler available from Cabot Corporation of Tuscola, Illinois. A variety of sizes are available. "Epoxy" refers to the conventional definition of the product which is an epoxy resin mixed with a specific curing agent, usually a polyamine or polyepoxide mixed with a polyamine curing agent. MYLAR ® refers to a polyester of polyethylene terephthalate of DuPont, Inc. of Wilmington, Delaware. It is usually commercially available in sheet form of varying thicknesses. "Metal nitride or metal oxynitride" refers to any electrically conducting metal oxynitride of metals of Groups III, IV, V, VI or VII of the Periodic Table. Preferably the metal is a transition metal. More preferably, the metal is independently selected from molybdenum, nobium, tantalum, titanium, vanadium, zirconium, or combinations thereof, and is especially titanium or molybdenum. For the metal oxynitride, this structure does not describe a combination of M0 2 , M0 3 , M0 4 , etc. with MN, M 2 N, M 3 N, MN 2 etc. MNO describes a general formula M x N y O- wherein M is metal, preferably a transition metal wherein: x is between 0.7 and 1 .3, preferably between 0.9 and 1 .1 , more preferably about 1 ; y is between about 0.7 and 1 .3, preferably between about 0.9 and 1 .1 and more preferably about 1 ; and z is between about 0.7 and 1 .3, preferably between about 0.9 and 1 .1 and more preferably about 1 . For titanium oxynitride, this formula does not describe combinations of Ti0 2 , and TiN, or variations thereof. TiNO is a general formula Ti x N y O z wherein: x is between 0.8 and 1 .2, preferably about 1 ; y is between about 0.8 and 1 .2, preferably about 1 ; and z is between about 0.8 and 1 .2, preferably about 1 . "Metal oxide" refers to any electrically conducting metal oxide. "Mixed metal oxide" refers to an electrically conducting oxide compound comprised of two or more metal oxides, optionally mixed with a non-conducting compound. Dry Preunit Energy Storage Device Referring now to the drawings, and more particularly to Figure 1 thereof, there is illustrated a dry preunit of energy storage device 1 0 which is constructed according to the present invention. The energy storage device is first an assembled dry preunit 10. After filling the present cells with an aqueous or non-aqueous electrolyte, the exterior surface is sealed (fused) (e.g. heat, uv), to form device which is then electrically charged. The device preunit 10 generally includes a plurality of cells, such as the cells 1 10, 1 1 2 and 1 14, which are formed, prepared, and stacked according to the teaching of the present invention. Figure 1 A U.S. Patent 5,464,453 (not shown) illustrates an assembled view of the electrical storage device preunit, formed of twelve superposed cells. It should however be understood to those skilled in the art, after reviewing the present specification that any different number of cells can be used. For simplicity of illustration, Figure 1 is an exploded view of the preunit 10, showing only three exemplary cells 1 1 0, 1 1 2 and 1 14. The cells have generally similar design and construction, and therefore, only the cells 1 14 and 1 1 2 are described in detail (in relation to Figures 2, 2A, and 3 of U.S. Patent 5,384,685). The cell 1 14 includes a first electrically conductive external electrode or end plate 1 1 1 A, and a second internal, electrically conductive bipolar electrode 1 1 1 B. Both electrodes 1 1 1 A and 1 1 1 B are spaced apart at the edges by means of two dielectric or electrically insulating gaskets 1 21 and 1 23. When the first and second electrodes 1 1 1 A and 1 1 1 B, and the insulating gaskets 1 21 and 1 23 and the electrically conducting porous material (oxide) layers 1 1 9 and 1 20 are bonded together to form the cell 1 14, a central air filled gap is formed by these elements. When the preunit 1 0 is ready to be used, the gap 1 30 is filled with an electrolyte (not shown) to produce device. For this purpose, an exemplary access or fill port, and is formed between the gaskets 1 21 and 1 23, in order to allow the electrolyte to fill the gap. The fill port is formed by means of a tab or cord 1 1 7A, which is inserted between the gaskets 1 21 and 1 23, prior to fusing or bonding the gaskets 1 21 and 1 23. When the gaskets 1 21 and 1 23 are heated, the cord 1 1 7A becomes surrounded by the reflow gasket material, which causes the outline of fill port to be formed. The two gaskets become a fused polymer mass covering a minimum of the active electrically conducting coating layers 1 1 9 and 1 20. Metal nitrides — The metal nitrides or mixed metal nitrides which are known in the art are also used to store energy in the present device by replacing part of all of the metal oxides or mixed metal oxides as described herein. Metal nitrides include, for example, any of the metals found in the Periodic Table. The dry preunit is assembled according to the patents cited herein, primarily U.S. Patent 5,464,453. It is then evacuated and filed with appropriate liquid electrolyte and sealed to create the electrical storage device. Mo 2 N - The molybdenum nitride (Mo 2 N) and molybdenum carbide (Mo 2 C) ceramic electrodes are both excellent embodiments for an ultracapacitor. Both ceramics are electronically conductive, have very high specific surface area (e.g. > 100 m 2 /g), e.g. between 50 and 250 m 2 /g, have mechanical, stability and chemical stability as well as electrochemical stable in aqueous and nonaqueous electrolytes. Mo 2 N electrodes are prepared by first spray pyrolysis or dip coating pyrolytic hydrolysis of (MoCI 5 + isopropyl alcohol) precursors onto metal foils or sheets at, e.g. titanium, tantalum or zirconium followed by heating at elevated temperatures, e.g. preferably, about 250 to 550°C preferably about 300°C, for about 1 to 20 hr, preferably 5 hr, to form oxide ceramics, i.e. Mo0 3 and Mo0 2 . The high surface area ceramic oxides are then converted to Mo 2 N by reacting Mo0 3 or Mo0 2 with ammonia, NH 3 , at elevated temperatures, e.g. > 300°C preferably about 300 to 500°C (or 800°C), for between about 1 to 20 hr, preferably 5 hr in a constant temperature furnace. In addition to NH 3 , a mixture of N 2 + H 2 gases can also be used as a reactant for the conversion of oxides to nitrides. Metal carbides — The metal carbides or mixed metal carbides which are known in the art are also used to store energy in the present electrical storage device by replacing part or all of the metal oxides or mixed metal oxides which are described herein. Metal carbides include any of the metals of the Periodic Table. The metal carbides are prepared by adaption of the process described above for metal nitrides. For example, Mo 2 C ~ When carbon mono-oxide, CO, is substituted for NH 3 , the carbide of molybdenum is produced. Considering now the electrodes 1 1 1 A and 1 1 1 B in greater detail, the methods of manufacturing them will be described later. One difference between the electrodes 1 1 1 A and 1 1 1 B is that the electrode 1 1 1 A optionally includes a tab 1 60A, for connection to a power source (not shown). A further, but optional distinction between the electrodes 1 1 1 A and 1 1 1 B, is that the electrode 1 1 1 A includes one porous electrically conductive coating layer 1 1 9, which is deposited on a support material or structure 1 1 6, while the bipolar electrode 1 1 1 B includes two porous coating layers 1 20 and 1 31 , which are deposited on either or both sides of the support material or structure 1 1 8. As such, the electrode 1 1 1 B is a true bipolar electrode. It should be understood that both sides of the electrode 1 1 1 A are preferably coated with porous electrically conductive layers. Yet another optional distinction between the electrodes 1 1 1 A and 1 1 1 B lies in the rigidity of the support structures 1 1 6 and 1 1 8. The electrode 1 1 1 A, acting as an external end plate, should preferably have a more rigid construction, so that it imparts sufficient rigidity to the overall structure of the energy storage device. The electrode 1 1 1 B and other similar internal electrodes do not necessarily need to be as rigid as the external electrode 1 1 1 A. Nonetheless, when the device is large, additional support structure is required, and the internal electrodes, i.e. 1 1 1 B, are used as additional support structure. In this case, it is desirable to rigidify the internal electrodes, i.e. 1 1 1 B. As a result, the support material 1 1 6 is generally thicker than the support material 1 1 8. In the preferred embodiment, the support material 1 1 6 has a thickness of about 1 0 mils (0.0254 cm), while the support material 1 1 8 has a thickness of about 1 mil (0.00254 cm). Other values could alternatively be selected. The electrodes 1 1 1 A, 1 1 1 B and the remaining electrodes of the storage device are sized and dimensioned according to the desired application, without departing from the scope of the invention. For instance, in one application, the device is miniaturized, e.g. for a cardiac defibrillator. While in another application, the overall volume of the device is one cubic meter or even greater, e.g. for an electric vehicle. The dimensions of the electrodes determine the overall capacitance of the storage device. Considering now the coating layers 1 1 9 and 1 20 in greater detail, the methods of forming them are described below. In the preferred embodiment, the coating layer 1 1 9 includes a plurality of microprotrusions, while the coating layer 1 20 does not include such microprotrusions. It should be understood, however, that the coating layer 1 20 could alternatively be designed similarly to the coating layer 1 1 9, without departing from the scope of the invention. Considering now the coating layer 1 20, it serves a similar function as the coating layer 1 1 9, and is deposited on the side of the electrode 1 1 1 B, which faces the inner side of the first electrode 1 1 1 A. In the preferred embodiment, the coating layer 1 20 does not include microprotrusions. In an alternative embodiment of the preunit 1 0, the coating layers 1 1 9 and 1 20 are similarly constructed, and include microprotrusion layers. Considering now the gaskets 1 21 and 1 23, the methods of producing them will be described later. The gaskets 1 21 and 1 23 are generally identical, and are arranged in registration (adjacent and superposable) with each other. For brevity, only the gasket 1 21 will be described in greater detail. The gasket 1 21 includes a solid peripheral section and a hollow central section. In the preferred embodiment, the cord 1 1 7A, or a part thereof, is placed between the gaskets 1 21 and 1 23, and extends across the hollow section, of the gaskets, and protrudes outside the peripheral section. In another embodiment, the cord does not extend across the central section of the gaskets, and only a part of the cord is sandwiched between the gaskets and extends beyond both edges of one side of the gasket. Methods of Manufacturing the Energy Storage Device Referring to Figure 1 , a general description for the preferred method to produce the dry pre-unit 1 0 and of the filled and sealed energy storage device, is as described in U.S. Patent 5,464,453. The porous coating thickness is between about 1 and 10,000 μ, preferably between about 1 and 200 μ, and more preferably between about 5 and 50 μ. When the preunit device 10 is filled with an electrolyte, it becomes ready to be charged to become device 10A. The main criterion for the electrolyte is to be ionically conductive and have bipolar characteristics. The boundary or interface region between the electrode and the electrolyte is referred to in the field, as the "double layer" , and is used to describe the arrangement of charges in this region. A more detailed description of the double layer theory is found in "Modern Electrochemistry", by Bockris et al, volume 2, sixth print, chapter 7 ( 1 977). The surface area of the coating layer affects the capacitance of the electrolyte-filled device. If for instance, the surface enhancement factor is between 1 ,000 to 20,000, and the double layer capacitance density is between about 10 to 500 microfarad per cm 2 of the interfacial surface area (i.e. the BET surface area), then surface enhancement capacitance densities of about 0.1 to 1 0 farads/cm 2 for the projected surface area of the electrode are obtained. Although coating with any surface enhancement value are used within the scope of the present invention, larger surface area coatings are more preferred because of the increased capacitance density. Coatings with surface areas between about 1 0 and 1 000 m 2 /cc are preferred, and preferred values between about 20 and 200 m 2 /cc, more preferably about 100 m 2 /cc. While the double layer theory is described herein, it should be understood that other theories or models, such as the proton injection model, could alternatively be used without departing from the scope of the present invention. Further, the exact surface area porosity and coating thickness can be adjusted and modified by one of skill in the art having this application to meet and achieve the objectives of this invention. The high surface area (porous) electrically conducting coating material, e.g., metal nitride or metal oxynitride, is applied onto the support material. 1 . Solution Methods - The porous coating material may originate from various reactive precursors in a solution or a sol-gel composition. Numerous methods of application of these precursor compositions are feasible; but not limited to the following. A curing, hydrolysis and/or pyrolysis process usually is performed to form the coating on the support. Pyrolysis of the metal salts is usually done in a controlled atmosphere (nitrogen, oxygen, water, and/or other inert and oxidative gasses) by means of a furnace and/or an infrared source. (a) Dip Coating - The electrode or support, is dipped into a solution or sol-gel, coating the support with a precursor coating, and subsequently cured by pyrolytic and other methods. Optionally, this process may be repeated to increase layer thickness. A preferred procedure is to dip the support material in a metal chloride/alcohol solution followed by pyrolysis at between about 250 and 500 ° C for 5-20 min in a 5-100% oxygen atmosphere. This process is repeated until the desired weight of coating is obtained. A final pyrolysis treatment at 250-450 ° C is done for 1 -10 hr. Typically about 1 -30 mg/cm 2 of coating is deposited onto a support for a capacitance density of around 1 -10 F per square centimeter electrode cross-sectional area. Another procedure is to create a sol-gel solution with ruthenium, silicon, titanium and/or other metal oxides and coat the support as above. By adjusting the pH, water concentration, solvent, and/or the presence of additives like oxalic acid, formamide, and/or surfactants the discharge frequency characteristics of the coating may be adjusted. High relative humidity during the pyrolysis step can be used to complete the conversion of starting material to oxide at lower temperatures. A procedure is to pyrolyze at about 300°C without control of humidity. However, an additional procedure is to maintain the relative humidity above about 50% during this pyrolysis at temperatures of about 350°C or below. (b) Spray Coating - The coating solution is applied to the support by a spray method, cured, and optionally repeated to increase the thickness. A preferred procedure is to apply the coating solution to the substrate at a temperature of 0- 1 50 ° C by means of an ultrasonic or other spray nozzle with a flow rate of around 0.1 -5 ml/min in a carrier gas composed of nitrogen, oxygen and/or other reactive and inert gases. The coating characteristics are controlled by the partial pressure of oxygen and other reactive gasses. (c) Roll Coating - The precursor coating is applied by a roll coating methodology, cured, and optionally repeated to increase the thickness. The coatings described above for dip coating are usable here. (d) Spin Coating - A spin coating methodology in the conventional art is used to apply the precursor coating, and optionally repeated to obtain the desired thickness. (e) Doctor Blading - A doctor blading methodology is used to apply the precursor coating, and optionally repeated to obtain the desired thickness. 2. Electrophoretic Deposition - The porous coating or precursor coating is applied to the support by electrophoretic deposition techniques, and optionally repeated to obtain the desired thickness. 3. Chemical Vapor Deposition - The porous coating or precursor coating may be applied by chemical vapor deposition techniques known in the art. (C) Electrode Coating Pretreatment It has been found that a number of pretreatments (conditioning) or combinations thereof are useful to improve the electrical characteristics of the coating (e.g. electrochemical inertness, conductivity, performance characteristics, etc.). These treatments include for example: 1 . Steam - High temperature water or steam treatment controlled in atmospheres can be used to decrease the leakage current. A method procedure is to contact the coated electrode with water saturated steam in a closed vessel at between 1 50 and 325 ° C for between 1 to 6 hr. under autogenic pressure. 2. Reactive Gas - The coated electrode is contacted one or more times with a reactive gas such as oxygen, ozone, hydrogen, peroxides, carbon monoxide, nitrous oxide, nitrogen dioxide, or nitric oxide at between about ambient temperature and 300 ° C at a reduced pressure or under pressure. A preferred procedure is to contact the coated electrode with flowing ozone at between about 5-20 weight percent in air at between about ambient and 100 ° C and 0.1 -2000 torr pressure for 0.1 -3 hr. 3. Supercritical Fluid - The coated electrode is contacted with a supercritical fluid such as carbon dioxide, organic solvent, and/or water. A preferred procedure is treatment with supercritical water or carbon dioxide for 0.1 -5 hrs by first raising the pressure then the temperature to supercritical conditions. 4. Electrochemical Treatment - The coated electrode is placed in an aqueous electrolyte. The electrode is then switched to a cathodic current and the open circuit potential is driven back to a potential of between about 0.5V - 0.75V, preferably between 0.5 and 0.6 and more preferably about 0.5 V (vs. NHE) with out hydrogen gas evolution. 5. Reactive Liquid - The coated electrode is contacted with an oxidizing liquid such as aqueous solutions of hydrogen peroxide, ozone, sulfoxide, potassium permanganate, sodium perchlorate, chromium (VI) species and/ or combinations thereof at temperatures between about ambient to 1 00 " C for 0.1 -6 hr. A preferred procedure uses a 1 0-100 mg/l aqueous solution of ozone at 20-50 ° C for between a about 0.5-2 hr. followed by an aqueous wash. An additional procedure is to treat the coated electrode in a chromate or dichromate solution. (J) Post-Conditioning 1 . A number of post-conditioning reactive gas treatments of the stack or assembled stack or combinations thereof are useful to improve the overall and long term electrical characteristics of the electrode and resulting device. These include either before step (H) and/or after step (I) treatment with hydrogen, nitric oxide, carbon monoxide, ammonia, and other reducing gasses or combinations thereof at between ambient temperature and the T m of the gasket material at a reduced pressure or under pressure. 2. A second post conditioning commonly done in the art is to adjust the open circuit potential of the electrode after step (F) and stack the electrode in an inert atmosphere (e.g. Ar, N 2 ). This is done by using a cathodic current without hydrogen evolution. (K) Filling of the Dry Preunit The dry preunit is filled with an ionically conducting aqueous or non-aqueous electrolyte and includes neutral alkali metal halide salts. One electrolyte is approximately 30% sulfuric acid in water due to the high conductivity. Non-aqueous electrolytes based on propylene carbonate and ethylene carbonate are also used to obtain larger than 1 .2V/cell potentials. A preferred procedure for filling the dry preunit with liquid electrolyte is to place the preunit in a chamber, evacuate the chamber between about 1 torr to 1 microtorr, preferably about 250 mtorr to less than 1 torr, and introduce the electrolyte; thereby, filling the cell gaps with electrolyte through the fill ports. Alternatively, the preunit may be placed in the electrolyte and a vacuum pulled; thereby causing the gas in the cell gaps to be removed and replaced by the electrolyte. In addition, non liquid based electrolytes (e.g. solid and polymer) may be used. In those cases the electrode is coated with the electrolyte before ref low and a fill port is not required. The electrode capacitance density (C in units of F/cm 2 ) is roughly 1 F/cm 2 for every 10 μm of coating. Therefore, for large capacitance values a thicker coat is used. The device capacitance (C) is equal to the electrode capacitance density times the electrode area (A in units of cm 2 ) divided by two times the number of cells (n) (equation 1 ). The leakage current (i") is proportional to the electrode area, A' while the equivalent series resistance (ESR) is inversely proportional to the electrode area (eqn. 2). Typical values for i" are less than 20 μA/cm 2 . The total number of cells in a device (n) is equal to the cell voltage (V) divided by the total device voltage (V) (eqn. 3). Cell voltages up to about 1 .2 V can be used with aqueous based electrolytes. The device height (h), based on a cell gap (h') and a support thickness (h"), is determined from the number of cells and the electrode capacitance density in units of cm by equation 4. The device ESR is a function of the number of cells (n) times the cell gap (h') times the resistivity of the electrolyte (r) times a factor of about 2 divided by the area A' (equation 5). eqn. 1 C = C'A72n eqn. 2 i" a A'a 1 /ESR eqn. 3 n = V/V eqn. 4 h/cm = n(0.002C' + h' + h") eqn. 5 ESR « 2nh'r/A' Devices are constructed to meet the requirements of various applications by considering the voltage, energy, and resistance requirements. The following examples are not meant to be limiting in any way: For electric vehicle applications about a 100 KJ to 3 MJ device is used. A large voltage (about 100 to 1 000 V) large energy ( 1 -5 F/cm 2 ) storage device is used with an electrode area of about 100 to 10,000 cm 2 . For electrically heated catalyst applications for the reduction of automobile cold start emissions about a 10 to 80 KJ device is used. This device is about 1 2 to 50 V constructed with around 1 00 to 1000 cm 2 area electrodes of 1 -5 F/cm 2 . Optionally, a device consisting of several devices in parallel can be constructed to meet the electrical requirements. For defibrillator applications about a 200-400 V device with 0.5 to 1 0 cm 2 area electrodes of 1 -3 F/cm 2 are used. Metal Nitrides In the general procedure to prepare metal nitrides, the metal halide is dissolved or slurried in a volatile organic liquid, or mixture of liquids as is described herein. Alcohols are preferred. The metal sheet of a size and thickness is dipped into the liquid to coat both flat surfaces of the sheet. The coated sheet is then placed in an oven in the presence of oxygen or air at 1 50-400°C (preferably about 200°C) for between about 5 to 60 minutes (preferably between about 5 and 20 minutes) to produce the metal oxide and to remove the organic liquid. This cycle is repeated 10 to 100 times to obtain the desired thickness of the oxide on the sheet (5-10,000 μ) . The coated sheet is then annealed at 1 50 to 400°C for 1 to 3 hours to convert 95 % or greater of the chloride to the oxide. The coated sheet is then heated slowly at 40°C/minute or less in a nitrogen atmosphere to between about 500-800°C Once the coated sheet is heated to 500 to 800°C it is contacted with ammonia gas (or a mixture of hydrogen and nitrogen) at between 500 and 800°C for between about 1 to 6 hours (preferably about 2-4 hours) which produces the metal nitride film, e.g., 5 to 10,000 μ, preferably (5-100 micron). Generally, the maximum temperature for the Mo 2 N production is about 700°C, the temperature for the TiN production is about 800°C, and the temperature for Fe x N production (where x = 2, 3 or 4) is about 500-550°C Titanium Nitride ~ 1 M Titanium chloride (TiCI 4 ) in isopropanol solution is used for dip coating the film on a titanium (foil) substrate. The remainder of the process described herein for the molybdenum nitride is repeated except that the temperature of nitriding is at 800°C The titanium nitride has a 1 .2 voltage window; 0.23 F/cm 2; 23 F/g, about 30 m 2 /g (BET) in surface area. iron Nitride - 1 M iron chloride FeCI 3 , optionally with FeCI 2 in isopropanol solution is used for dip coating the film on a titanium (foil) substrate. The remainder of the process described herein for molybdenum nitride is repeated, except that the temperature of the nitriding occurs at 500-550°C, Iron nitride has a CV voltage window of 1 .2 volts, 0.20 F/cm 2; 75 F/g, and 30 m 2 /g (BET) in surface area. The x-ray diffraction (XRD) pattern result of molybdenum nitride film after about four to six hours reaction with ammonia gas is shown in Figure 2. It matches to the Joint Committee on Powder Diffraction Standards (JCPDS) computer data base of fee -Mo 2 N structure. Typical cyclic voltammetry (CV) test results of Mo 2 N in 3.5M H 2 S0 4 and 1 M KOH solutions at a scan rate of 10mV/sec are shown in Figure 3. The capacitance and specific capacitance data from CV testing are 1 .0 F/cm 2 , 1 25 F/g respectively, both in acid and alkaline solutions. The molybdenum nitride electrodes are stable through 6000 cycles. Comparing the continuous cycles of same materials in both acid and alkaline solution, Molybdenum ion dissolution measurement, leakage current test and package cell test demonstrate Mo 2 N is more stable in alkaline solution than in acid solution, but has a 0.7 V voltage window in alkaline solution, while it has a 0.8 V voltage window in acid solution. Brunaner-Emmett-Teller (BET) data yields a surface area of 1 6 m 2 /g for the Mo 2 N film. Molybdenum nitride is a candidate as an alternative material for ultracapacitor charge storage material. The advantages are low-cost, high-surface area, and conductive material. The disadvantages are that the nitride has a smaller voltage window compared to the mixed ruthenium and tantalum oxide, it has moderate mechanical adhesion which may cause some difficulty when packaging the cell, and it is marginally stable as an ultracapacitor charge storage material in aqueous solutions. Metal Oxynitride Formation and Performance Metal (e.g., titanium) oxide formation condition is judged by BET surface area, SEM pictures, XRD results and CV performance of the metal (e.g., titanium) oxynitride. The optimized sample is pyrolyzed at 200°C for 2 hours annealing after dip coated in 1 M TiCI 4 IPA solution. There is no titanium dioxide peak in the XRD patterns and the biggest crack in SEM picture. Although pyrolysis of the oxide at 1 50°C shows the highest BET surface area, these samples create a rutile structure of titanium dioxide which can not be nitrided further at 700°C Annealing at 300°C gives relatively lower capacitance, and annealing at 400°C gives very poor mechanical adhesion and low capacitance. After six hours of reaction in NH 3 flowing (22.5 L/min) and H 2 , (4.5 L/min flowing) gas atmosphere at 700°C at ambient pressure, the TiNO is produced. TiNO shows the BET specific surface area of 56 m 2 /g and the highest capacitance up to 1 .51 F/cm 2 , 79 F/g in 3.5M H 2 S0 4 and 1 .45 F/cm 2 , 75 F/g in 1 .OM KOH with a 1 .2 voltage window from CV curves (see Figure 4). The active ultracapacitor material cost is estimated to be reduced to about sixty-two cents per kilo-Joule. XPS (ESCA) Material Composition Analysis ESCA results of samples of TiNO after nitriding are listed in Table 1 . Carbon is the contamination on the surface. Argon is used for etching. The nitriding conversion is 38% based on the calculation from oxide to nitride conversion in this table. The products after nitriding at the conditions described above are named as titanium oxynitride (TiNO). TABLE 1 ESCA analysis of TiNO Element Ti 0 N C Ar Atomic 30 35 21 13 1 Percent Rutherford Backscatering Spectroscopy (RBS) Analysis and SEM Micrographs The RBS result (Table 2) is consistent with the ESCA result for TiNO samples. The ratios of Ti:0:N are about 1 : 1 : 1 . These data support the hypothesis of titanium oxynitride. RBS analysis of the samples of different capacitance show the same atomic percentages of Ti, 0 and N. This implies that the capacitance is not related to the atomic percentages of the sample. It also shows no relation of sample composition with dip coating methods. Figures 5A to 5F show the SEM pictures of these three different capacitance samples, which reveal the different surface morphology. TABLE 2 RBS result of TiNO samples in atomic percentage Capacitance S.C. Surface Ti 0 N (F/cm 2 ) (F/g) Area (%) (%) (%) (m 2 /g) 0.3 20 30 0.37 0.33 0.30 0.5 38 37 0.41 0.29 0.30 0.9 65 41 0.38 0.32 0.30 1 .5 75 56 0.40 0.30 0.30 Capacitance Effect by Surface Area - Although the capacitance is not related to the composition of the material, it is clear that the capacitance is related to the BET specific surface area from Table 2. Figure 20 reveals this fact that the capacitance is proportional to the material specific surface area by plot the data under different nitride reaction conditions. The titanium oxynitride shows the double layer capacitor phenomena. Comparison CV Cycles in Different Electrolytes - TiNO The CV test starting material capacitance is 1 .02 F/cm 2 in 1 M KOH, after 1 20 continuous CV cycles ( 1 6 hrs) the capacitance decreased to 0.80 F/cm 2 in 1 M KOH, while the decrease was to 0.1 6 F/cm 2 in 3.5M H 2 S0 4 . The TiNO film seems to be stable only in alkaline solution. XRD result shown in Figure 7A is a titanium oxynitride fresh sample (a) and after 1 20 CV cycles in both acid solution (Figure 7B) and alkaline solution (Figure 7C). The peaks of fresh sample and the sample after 1 20 CV cycles in KOH solution show the peak position in between TiO and TiN. The sample after 1 20 CV cycles in 3.5M H 2 S0 4 shows two types of titanium dioxide (rutile and anatase), as well as titanium metal. The SEM picture of a fresh sample titanium oxynitride (Figure 8A) and after 1 20 CV cycles ( 1 6 hours) in alkaline solution (Figure 22B) and acid solution (Figure 22C). The morphologies are the same of the fresh sample and the sample after 1 20 CV cycles in KOH. The sample after 1 20 CV cycles in 3.5M H 2 S0 4 shows a totally different structure which is consistent with XRD results: (a) Fresh sample (b) After CV cycles in KOH (c) After CV cycles in H 2 S0 4 . After six charge/discharge cycles, the electrolytes are analyzed by inductively coupled plasma (ICP) spectrometry. The Ti-ion concentration in 6M KOH is 3 ppm, but in 3.5M H 2 S0 4 it is 853 ppm. This huge difference in concentration indicates that TiNO film is much more stable in alkaline solution than in acid solution. Titanium Oxynitride Adhesion and Cohesion Test (Qualitative) There are no standards to test the film adhesion and cohesion yet. The bend test is: simply hold the film, and bend the corner 1 80 degrees, then bend it back. The SEM is used to take magnified pictures (see Figures 9A and 9B). The width of cracks, and the straightness of the crack line can approximately represent the cohesion and the adhesion of the films. It is found that TiNO has cracks about five times wider than RuTaO x . Zirconium and Manganese as Cementation Materials The samples of 1 5 % to 65% Zr mixed TiNO are pyrolyzed at 200°C in 2 hrs. All samples show good adhesion. Specific surface area and the capacitance decrease as the Zr amount increases, which is interpreted that Zr is not an active material. Using a 1 .5M TiC 1 4 solution, mixing with either 0.5, or 10% Mn are dip coated on Ti substrates. After pyrolysis and nitriding, the more Mn added, the poorer the cohesion is since the Mn changes the original morphology from SEM photographs (Figure 24). The BET specific surface area decreases from 55 to 1 6 m 2 /g when Mn amount increases rom 0 to 10% . Reliability of Nitriding Reaction Test Eleven samples are nitrided under the same conditions. These samples were divided into two groups: TiNO and TiNO + 1 %Mn. Except for two runs which failed, all the tests have a similar capacitance as listed in Table 3, and all of them are completely nitrided in the reaction as shown by XRD patterns. Ignoring the two failed runs, the average capacitance of TiNO is 0.56 ± 0.05 F/cm 2 , which yields a specific capacitance of 46 ± 4 F/g. The average capacitance of TiNO + 1 %Mn is 0.63 ± 0.05 F/cm 2 , which yields the specific capacitance of 47 ± 4 F/g. Both materials have relative errors of 8 %, or deviation of 7% . These errors consist of three parts: manually dip coating of oxide sheets; different runs of nitride reaction; capacitance calculations from CV graphs. The capacitance from different oxide sheets varies comparing sheet A and B or A' and B' are found in Table 3. TABLE 3 Capacitance of TiNO and TiNO + 1 % Mn Addition of other metal oxides to enhance adhesion of titanium oxide In the standard RuTaOx system, the addition of tantalum oxide acts as a dispersing agent which increases surface area, improving specific capacitance and smoothing out the surface of the coated sheets. But because of cost, TaCI 5 is not economical in the TiNO system and replacement materials such as MnCI 2 and ZrCI 4 were investigated. Incorporation of MnCI 2 and ZrCI 4 into the precursor solution improved the adhesion of the coating material and smoothed out the surface of the electrodes. A parametric study was performed on both additives to see which metal oxide improves adhesion more as well as retains or increases the specific surface area of Ti0 2 . The experiments entailed coating the electrodes using the standard coating process at 200°C for 2 hrs in air. With the addition of either metal oxide to the precursor solution at the optimum condition, the structure of the material remained amorphous. The addition of 1 to 10% MnCI 2 to the 1 M TiCI 4 /IPA solution improved the adhesion of the coating but lowered the surface area. (Se Figures 24A, 24B and 24C). The more MnCI 2 was added to the solution, the lower the surface area became. Therefore only a limited amount ( <5 %) of MnCI 2 was added to the system. The advantage of using MnCI 2 over ZrCI 4 is that all phases of Mn0 2 are conductive unlike Zr0 2 where its presence can lower the capacitance of TiNO. Different amounts of ZrCI 4 were added to the precursor solution of ( 1 M TiCI 4 /IPA) to further improve adhesion. The amount of the additive varied from 1 5 to 65%. The adhesion was very good for up to 35 %, but flaking was observed in the electrodes with the higher ZrCI 4 content. The surface of the electrodes was very smooth while the specific surface area increased with increasing ZrCI 4 content until a maximum was reached and then started to continuously decrease. After nitriding these electrodes, the resulting material was not very conductive therefore the amount of ZrCI 4 that should be added into the precursor solution should not be beyond 5 % . In the standard coating process described herein, there is no control over the environmental conditions. In a controlled pyrolysis reacor, more control over the conditions such as temperature, humidity and air flow rate is used. When using the controlled pyrolysis reactor, several halide coated sheets are dried and annealed at the same time. Pre-heated dry air flows through the reactor allowing temperature uniformity and control. Humidity, oxygen content, airflow rate and temperature at the inlet and outlet of the reactor as well as in different locations in the reactor zone, are tracked. By controlling these variables, there is obtained better adhesion of the coating material to the substrate, and the surface of the electrodes is much smoother. When applying the standard coating process in high humidity environments, the surface of the coated sheets becomes uneven due to particle build-up. this build-up usually flakes off on contact, and the uneven surface causes problems for packaging. The reactor was used to synthesize a Ti0 2 film using the 1 M TiCI 4 /IPA solution on a Ti substrate with 1 5 coats annealed at 200°C for 2 hours. In the reactor, the coating process is different than the standard process. The electrodes remain inside the reactor during both steps as compared to the standard process where the electrodes are removed from the drying oven to the annealing oven thus being exposed to the surrounding conditions. The coating process in the reactor consists of drying at 75 °C for 1 0 min. ramping (increasing) the temperature up to 200°C holding for 10 min. and then cooling to about 75 °C The adhesion of the coating material is much better in the reactor than the standard coating process. But the specific surface area was lower (25 m 2 /g vs. 36 m 2 /g) due to the control over the processing conditions (i.e., coating process, temperature, humidity and air flow rate). The addition of steam into the process improves the specific surface area of Ti0 2 . Using the 1 M TiCI 4 /IPA on 5 mil Ti with 1 5 coats at 200°C for 2 hours, the reactor processing conditions were as follows: dip in the precursor halide solution, dry at 75 °C for 10 minutes then ramp up to 200°C and add steam 45 cubic feet per minute (CFM), 1 to 30% relative humidity for 1 0 minutes (in between each coat only). After adding 1 5 coats of halide, the product is annealed at 200°C for 2 hours. At 200 °C, the maximum relative humidity attainable in the reactor was in the range of 1 to 1 .6% . although this may not be considered a 'humid' environment, these conditions have shown a distinct difference in the specific surface area of the electrode. The specific surface areas of the Ti0 2 electrode process in three different methods at the same conditions ( 1 M TiCI 4 /IPA; 5 mil Ti; 1 5 coats; 200°C; 2 hour anneal) are: standard coating process 36 m 2 /g reactor w/out steam 25 m 2 /g reactor w/steam 90 m 2 /g With the addition of steam, the specific surface area is almost three times higher than without steam although the loading is the same for all three conditions (about 8 mg/cm 2 ). All results have been reproducible at different conditions. Nitriding Ramping Rate and Reaction Temperature. Temperature programmed reaction is a slow increasing (ramping) rate in order to produce the maximum surface area. Different ramping rates are studied to optimize nitriding conditions. Capacitance data is listed in Table 4. When the temperature is increasing at less than the 3.5 hour from 25 °C to 700°C, the slower rate gives better result. More than 3.5 hrs of ramping rate shows no extra advantage. The nitriding reaction at 700°C yields an oxygen to nitrogen ratio of 1 : 1 in the TiNO sample. At 800°C, the nitriding reaction is more complete, with a N:0 ratio of 4: 1 . The sample color is close to gold. The capacitance is 23 F/cm 2 (BET surface area 26 m 2 /g), about half the capacitance and half the surface area compared to nitriding at 700°C (0.54 F/cm 2 , 59 m 2 /g). TABLE 4 The relation of ramping rate and capacitance Ramp Rate 0 1 .9 3.5 7.0 14.0 (hr) Reaction 4 4 4 4 4 Time (hrs) Capacitance 0.32 0.42 0.54 0.50 0.55 (F/cm 2 ) Impedance Measurement and Leakage Current Test in a Single Test Tube Cell The AC impedance measurement is carried out in a glass test tube. Two pieces of the same material are cut the same size (2 cm 2 ) . These two pieces are separated by a glass-paper separator which is dipped in the electrolyte. The AC impedance equivalent series resistance (ESR) is shown in Figure 25. At high frequency the TiNO film in alkaline medium has the same ESR as RuTaO x film in acid. Both of them are about 0.4Ω in single test tubes. The leakage current test is carried out that two pieces of TiNO which are cut to about 4 cm 2 and set separately in a test tube. This material is safe to charge up to 1 .2V. After the charge to 1 V in 1 M KOH, the leakage current data are shown in Figure 26. At least 4 hours is needed to achieve the so called "leakage current" . The ESR is the same value ( 1 .3Ω) before and after test. The leakage current in sulfuric acid is three times higher than in potassium hydroxide. The leakage current tet of different charge voltages are listed in Table 5. TABLE 5 Leakage current test in 1 M KOH Voltage Electrode Capacitance Leakage Current at 30 min. (V) (F/cm 2 ) (μA/cm 2 ) 0.5 0.36 25 0.7 0.45 39 0.9 0.53 69 1 .0 0.64 89 1 .1 0.73 1 1 5 1 .2 0.84 134 Packaged Titanium Nitride Ultracapacitor and After Test Analysis The first five-cell stack of titanium oxynitride ultracapacitors were packaged in 1 2.9 cm 2 size with 1 M KOH electrolyte. After charging to 5V using 99 mA charge/discharge current, the output energy and power are 0.8J and 0.2W respectively. This TiNO material for packaging purposes has a CV capacitance of 0.5 F/cm 2 . After EDM cut the material it is washed in 1 M KOH and Dl water, and has a capacitance of only 0.3 F/cm 2 . SEM pictures show some "holes" and "dusts" on the surface (Figures 27A, 27B and 27C). The charge capacitance of ultracapacitor to 1 V is 0.2 F/cm 2 per electrode. The first TiNO five-cell ultracapacitors last several hundred cycles. The ESR starts at 200 MΩ, then increases to several kΩ. The XRD shows oxide patterns on some sides of electrode sheets. The BET specific surface area of electrodes are: original 43 m 2 /g, both sides TiNO 46 m 2 /g, and one side Ti0 2 one side, TiNO 31 m 2 /g. The SEM pictures clearly show that when Ti0 2 ball cluster involved, the TiNO structure disappeared. (Figure 14A and 1 4B). The hypothesis is that there must be a electrochemical reaction happening during charge and discharge of the device. What causes this to happen appears to be a short in between some sheets. Then, there is an over charge in between the sheets. TiNO + 2H 2 0 + e → Ti0 2 + NH 3 + OH ' (4) The second packaging material for 1 2.9 cm 2 has a 1 .0 F/cm 2 capacitance from the CV test. After over 3000 cycles with charge and discharge current at 99 mA, the charge efficiency is kept over 90%. Ragone plots of single cell device is shown in Figure 1 5. The charge current is vary from 99 mA to 800 mA which corresponds to the discharge time vary from 35 to 0.3 seconds. The energy density and power density are calculated using active material weight only. Substantially Neutral Aqueous Electrolyte As has been stated elsewhere in this application, the use of strong aqueous acid or strong aqueous base in conjunction with the metal oxides, metal carbides, metal nitrides, metal oxynitrides or combinations thereof may not have long term stability in the presence of these aqueous electrolytes. This application claims substantially neutral salt aqueous electrolytes. Thus those electrolytes having a pH value of between about 6 and 8, preferably between about 6.5 and 7.5, more preferably between about 6.8 and 7.2 and especially about 7 are used. The salts used to produce the substantially neutral aqueous electrolyte are selected from the alkali metal halides. Preferred salts include the potassium and sodium chlorides and bromides, and a more preferred salt is potassium chloride. The concentration of the salts is usually between about 0.5 and 4.0M, preferably between about 1 .0 and 4.0M, more preferably between about 2.0 and 3.5M, and especially between about 3.0 and 3.5M. As is described in the Examples the metal nitride and metal oxynitride - containing electrodes are very useful in the presence of these substantially neutral electrolytes. The corrosion and degradation of the cell under operational conditions is greatly reduced or eliminated. In fact, the TiNO electrode with 1 M KCI is still functioning well after being charged and discharged more than 5,000 cycles at between 0 and 1 .6 volt per cell. This is the highest voltage yet reproducibly observed for this type of cell. Most surprising is the fact that the TiNO electrode with a 1 M KCI electrolyte is successfully charged and discharged at 1 .6V. The maximum that a double layer cell for long term use can be charged is usually about 1 .1 V. The metal nitride and metal oxynitride have comparable high surface areas which facilitate the storage of electrical energy. The coating )(e.g. nitride and/or oxynitride) is porous and composed of mosly micropores (diameter < 1 7A). Large 0.1 -1μm wide cracks are present on the surface protruding to depths as thick as the coating. However, greater than 99% of the surface area arises from these micropores. The average diameter of these micropores are around 6-1 2 A. In addition the micropores, a narrow distribution of mesopores (diameter < 1 7-1 000A) having a diameter of about 35 A is created. These treated electrode coatings have 85-95 % of the surface area arising from the micropore structure. Pore size distribution can be varied. The effective high surface area of the coating is 1 ,000 to 10,000 to 100,000 times larger than the projected surface area of the electrode as a monolith. Molydenum Nitride and Titanium Oxynitride Material Stability Test Two TiNO materials have been used for packing ultracapacitor devices. One has capacitance of 0.8 F/cm 2 while the other has 0.2 F/cm 2 . From Figure 30, it is clear that all device capacitance from charge/discharge test and material capacitance from CV test decayed during the cycles. Device tests showed decay faster than material CV tests because they are the closed system. Even small amount of gas evolution may damage the whole device. The data listed on the Figure 30 is the capacitance at 3000 cycles versus to the first few cycles. TiNO material decays much faster than RuTaO x material. One possible explanation is that TiNO not only has small layered cracks, but also has large deep cracks through down to the substrate (Figures 31 A and 31 B) . Thus, the substrate corrosion become a serious problem. The titanium oxynitride produced has a surface area of about 10 to 60 m 2 /g, preferably about 20 to 56 m 2 /g. Molybdenum nitride with tantalum oxide - Under certain circumstances, the combination of a transition metal nitride and tantalum oxide produces a high surface area layer having 30 to 50% better adhesion to the metal substrate characteristics than does the nitride alone. Preferably, a metal halide and the tantalum halide and mixed in about a 1 : 1 atomic ratio in isopropanol as is described herein coated multiple times, as a film on a substrate, dried, annealed and pyrolyzed. The resulting high surface area metal nitride-tantalum oxide has stronger adhesive to the substrate of 30 to 50 or 100% greater properties. Summary - Titanium oxynitride (TiNO) is an ultracapacitor energy storage material. The active material cost is presently about 62 cents per kilo-Joule. The performance of TiNO as an ultracapacitor material data is described. The more coats of oxide- oxynitride, the thicker the film the higher surface area and the higher the capacitance. But, the more coats, the poorer the cohesion. The adhesion and cohesion properties are improved when Zr is mixed in TiNO, but Zr is not an active material. COMMERCIAL APPLICATIONS Commercial applications of these metal nitride or metal oxynitride electrodes are found in U.S. Patent 5,464,453. Fabrication of Dry Preunit The following examples are presented to be descriptive and explanatory only. They are not to be construed to be limiting in any manner. General: Molybdenum chloride is obtained from Alfa Aesar and is used without further purification. Titanium chloride is also obtained from Alfa Aesar and is used without further purification. Iron chloride (FeCI 3 ) or (FeCI 2 ) are also obtained from Alfa Aesar and are essentially free of water. EXAMPLE 1 METAL NITRIDE (a) A solution (or slurry) of MoCI 5 about 10% by weight in isopropanol is prepared. A thin sheet of titanium is dip coated, first dried in air then at 70°C for about 10 min. The electrode is then heated in air or oxygen at about 300°C for about 5 hr, and Mo0 3 and Mo0 2 are formed. The sheet is coated, dried and heated several times to obtain the desired thickness of Mo0 3 and Mo0 2 . Optionally, the electrode is then annealed at 300°C for 3 hr. The pyrolyzed electrode is cooled to ambient temperature then heated in a flowing ammonia atmosphere at 1 atm at 350°C for about 5 hr. The Mo 2 N coated electrode is obtained. When a capacitor is formed by wet construction, dry construction, or fill port construction as described herein, e.g. Examples 1 -22 of U.S. Patent 5,464,453 and filled with suitable electrolyte, a useful high energy long-life energy storage device is obtained. (b) When Example 1 (a) is repeated except that the ammonia is replaced with a mixture of N 2 and H 2 , the corresponding useful Mo 2 N electrode and energy storage device is obtained. EXAMPLE 2 METAL CARBIDE (a) A solution (or slurry) of MoCI 5 about 10% by weight in isopropanol is prepared. A thin sheet of titanium is dip coated, first dried in air then at 70°C for about 1 0 min. The electrode is then heated in air or oxygen at about 300°C for about 5 hr, and Mo0 3 and Mo0 2 are formed. The sheet is coated, dried and heated several times to obtain the desired thickness of Mo0 3 and Mo0 2 . Optionally, the electrode is then annealed at 300°C for 3 hr. The pyrolyzed electrode is cooled to ambient temperature then heated in a flowing carbon monoxide atmosphere at 1 atm at 350°C for about 5 hr. The Mo 2 C coated electrode is obtained. When a capacitor is formed by wet construction, dry construction, or fill port construction as described herein, e.g. Example 1 , and filled with suitable electrolyte, a useful high energy long- life energy storage device is obtained. EXAMPLE 3 Molybdenum Nitride Mo 2 N - Molybdenum chloride is dip coated onto a Ti sheet, which was pre- etched in hot HCI as described in U.S. Patent 5,464,453. The 1 M molybdenum chloride in isopropanol film is first converted to molybdenum oxide in an oven by pyrolysis at temperatures between about 1 50-400° C for between about 5 and 60 minutes. The dip coating and oxidation and removal of isopropanol is repeated for 1 5 times. The oxide is then heated for 3 hours at 200°C to convert the 95 % or greater of the chloride to the oxide. The oxide is then converted to nitride via flowing NH 3 gas (1 3 l/min) over the oxide sheets at a temperature of about 700° C. This molybdenum nitride material is characterized by XRD, SEM, EDAX and AES. The ultracapacitor performance of Mo 2 N material is evaluated by cyclic voltammetry (CV), package cell charge-discharge cycles and leakage current measurement using KOH and H 2 S0 4 . EXAMPLE 4 Molybdenum Nitride (with Tantalum Oxide) Molybdenum chloride and Tantalum chloride TaC 5 (1 : 1 atomic ratio) are combined in isopropanol. The procedure of Example 1 is then repeated. The Mo 2 N/TaO x layer formed has better adhesion properties (at least 30% or greater) than without tantalum. This high surface area layer also has improved electrical storage properties, the voltage window expands to 1 .1 volt, for example. EXAMPLE 5 Titanium Nitride (a) Titanium chloride ( 1 M) in isopropanol is prepared. A titanium foil (flat sheet) substrate is dipped into the titanium chloride solution and coated. This coated foil is placed in an oven in air at 200°C for 10 min to convert the chloride to the oxide. The titanium chloride coated foil is removed from the oven and cooled to 20°C This coating and heating is repeated 1 5 times until the desired level of coating on the foil. The film is then post heated for 2 hr at 200°C to convert 95% or greater of the chloride to the oxide. The titanium oxide is then contacted with flowing ammonia ( 1 0-20 l/min) at 800°C for 4 hr. The titanium nitride film adheres well to the titanium sheet. The article is ready to be tested with electrolyte and/or used as an electrode in a double layer capacitor as described in U.S. Patent 5,464,453. (b) Example 5(a) is repeated except that hydrogen gas (1 -5 l/min) is combined with the ammonia at greater than 800°C for 4 hrs. The resulting metal nitride has similar properties. EXAMPLE 6 Iron Nitride A titanium substrate foil was coated with 0.7 M ferrous chloride-ferric chloride (FeCI 2 + FeCI 3 ) solution of isopropanol. The sheets were dip coated 1 5 times and dried in a reactor at 75 °C for 10 min then pyrolysis at 200°C for 1 0 min. The coated substrate is then heated up to 500°C The substrate is contacted with ammonia gas (flowing) ( 1 0-20 L/min) at 500°C for 4 hr. The Fe x N where x is 2,3,4 films produced is determined by XRD. The Fe x N coating has good adherence to the substrate. In an electrode configuration with 1 M KOH, it has a specific capacitance of 30 F/g. EXAMPLE 7 Molybdenum Oxynitride (a) Mo 2 NO - Molybdenum chloride is dip coated onto a Ti sheet, which was pre-etched in hot HCI as described in U.S. Patent 5,464,453. The 1 M molybdenum (penta) chloride in isopropanol film is first converted to molybdenum oxide in an oven by pyrolysis at temperatures between about 1 50-400° C for between about 5 and 60 minutes. The dip coating and oxidation and removal of isopropanol is repeated for 1 5 times. The oxide is then heated for 3 hours at 200°C to convert the 95 % or greater of the chloride to the oxide. The oxide is then converted to the oxynitride via flowing NH 3 gas ( 1 3 l/min) over the oxide sheets at a temperature of about 700° C. This molybdenum oxynitride material is characterized by XRD, SEM, EDAX and AES. The ultracapacitor performance of Mo 2 NO material is evaluated by cyclic voltammetry (CV), package cell charge-discharge cycles and leakage current measurement using KOH and H 2 S0 4 . (b) Similarly, when Example 7(a) is repeated except that the molybdenum chloride is replaced with a stoichiometrically equivalent amount of niobium chloride a corresponding amount of niobium oxynitride is obtained. (c) Similarly, when Example 7(a) is repeated except that the molybdenum chloride is replaced with a stoichiometrically equivalent amount of vanadium chloride a corresponding amount of vanadium oxynitride is obtained. (d) Similarly, when Example 7(a) is repeated except that the molybdenum chloride is replaced with a stoichiometrically equivalent amount of tantalum chloride a corresponding amount of tantalum oxynitride is obtained. (e) Similarly, when Example 7(a) is repeated except that the molybdenum chloride is replaced with a stoichiometrically equivalent amount of titanium chloride a corresponding amount of titanium oxynitride is obtained. (f) Similarly, when Example 7(a) is repeated except that the molybdenum chloride is replaced with a stoichiometrically equivalent amount of zirconium chloride a corresponding amount of zirconium oxynitride is obtained. EXAMPLE 8 Titanium Oxynitride (a) Titanium chloride ( 1 M) in isopropanol is prepared. A titanium foil (flat sheet) substrate is dipped into the titanium chloride solution and coated. This coated foil is placed in an oven in air at 200°C for 1 0 min to convert the chloride to the oxide. The titanium chloride coated foil is removed from the oven and cooled to 20°C This coating and heating is repeated 1 5 times until the desired level of coating is on the foil. The film is then post heated for 2 hr at 200°C to convert 95 % or greater of the chloride to the oxide. The titanium oxide is then contacted with flowing ammonia ( 10-20 l/min) at 700°C for 4 hr. The titanium oxynitride film adheres well to the titanium sheet. The article is ready to be tested with electrolyte and/or used as an electrode in a double layer capacitor as described in U.S. Patent 5,464,453. (b) Similarly, when Example 8(a) is repeated except that the titanium tetrachloride is replaced with a stoichiometrically equivalent amount of niobium chloride a corresponding amount of niobium oxynitride is obtained. (c) Similarly, when Example 8(a) is repeated except that the titanium tetrachloride is replaced with a stoichiometrically equivalent amount of molybdenum chloride a corresponding amount of molybdenum oxynitride is obtained. (d) Similarly, when Example 8(a) is repeated except that the titanium tetrachloride is replaced with a stoichiometrically equivalent amount of vanadium chloride a corresponding amount of vanadium oxynitride is obtained. (e) Similarly, when Example 8(a) is repeated except that the titanium tetrachloride is replaced with a stoichiometrically equivalent amount of tantalum chloride a corresponding amount of tantalum oxynitride is obtained. (f) Similarly, when Example 8(a) is repeated except that the titanium tetrachloride is replaced with a stoichiometrically equivalent amount of zirconium chloride a corresponding amount of zirconium oxynitride is obtained. (g) Example 8(a) is repeated except that hydrogen gas (1 -5 l/min) is combined with the ammonia at 700°C for 4 hrs. The resulting metal oxynitride has similar properties. EXAMPLE 9 Use of Neutral Electrolyte, LiCI (CV Capacitance 0.39 F/cm 2 , 50 F/g) Two test tube single cells are tested to compare the performance of neutral electrolyte versus alkaline electrolyte. The titanium oxynitride layers are produced as described in Example 8 to a thickness of 0.05 mm. All electrodes are cut to 2 cm 2 size. Comparing Figure 1 8 to Figure 1 9 TiNO in LiCI neutral electrolyte has less capacitance and higher resistance than in KOH alkaline electrolyte. There is not much difference using different test methods as shown in Figures 1 8 and 1 9. Figure 20 shows the TiNO in LiCI electrolyte has less leakage current than in KOH electrolyte. After 10 cycles charging to IV, the capacitance, energy and efficiency date are as shown in Table 6. These values are consistent with the AC impedance data. Table 6 EXAMPLE 10 Comparison of Hydroxide and Chloride Electrolytes (CV Capacitance 0.25 F/cm 2 , 39 F/g) Six test tube single cells are tested to compare electrode performance in different electrolytes. The TiON layers are produced according to Example 8 to a thickness of 0.05 mm. All electrodes are cut to 2 cm 2 size. Figure 4 shows that TiNO ultracapacitor is very stable through 5000 charge/discharge cycles in neutral electrolytes (aqueous salt solution), because the capacitance deteriorates in alkaline electrolyte. The higher the concentration of alkaline electrolyte, the faster the deterioration of the capacitance occurs due to corrosion. The capacitance and energies in neutral electrolytes are lower compared to the alkaline electrolytes as shown in Figures 21 and 22. The AC impedance data show the same situation in Figure 23. Leakage current was tested using different equipment, these data in Figure 24 can be used as reference, but are not reliable as a comparison. ESR data are shown in Figure 25. The ESR of neutral electrolytes are higher when compared to alkaline electrolytes. In neutral electrolytes, the ESR decreased after a series test. This series includes: AC impedance test, a 1 8 hours leakage current test, and a 5000 charge/discharge cycle test. In 1 M KOH the ESR increases a little while in 6M KOH increases greatly after the tests. The TiNO in neutral electrolytes have a much longer life time. Figures 26 and 27 compare the first ten charge/discharge cycles of capacitance and energy in different electrolytes cells. The efficiency of cells having neutral electrolytes is higher than in cells having alkaline electrolytes. Especially, the energy efficiency reveal a big difference in Figure 28. High surface area, low cost material such as TiNO is very helpful as an ultracapacitor electrode material. Several TiNO devices (size 1 2.9 cm 2 ) have been produced and investigated for their ultracapacitor performance. The TiNO electrode material in neutral electrolytes is very stable and is charged successfully up to 1 .6V per cell. Thus, the energy density of TiNO ultracapacitor is comparable to the energy density of an RuTaO x ultracapacitor. EXAMPLE 1 1 TiNO Electrodes Two devices of TiNO electrodes (No. 1 ,2) are fabricated according to Example 8 as single cell devices. Cellulose sheets are used as separators which have 4.7 mil thickness, while glass paper has only a 2.3 thickness. Devices 1 and 2 are filled with 1 M KOH and 1 M KCI electrolytes, respectively. Fig. 28 shows their AC impedance frequency response data. Device No. 1 doesn't show electrical performance. After a leakage current test, the ESR increases to 32 ohms. In Device No. 2 discharge capacitance and energy are 0.6F and 0.2J, respectively. The coulomb efficiency, energy efficiency, ESR, output capacitance and energy are kept constant through 1 0,000 cycles. The initial and final ESR are 93 and 98 mohm. Device No. 4 is a single cell device using 6M KOH as electrolyte. The ESR is 1 80 mohm. Unfortunately, this device can not be charged to 0.5V. EXAMPLE 1 2 TiNO Electrodes With Hydroxide and Chloride Electrolytes Devices 5, 6, 7 having 6M KOH, 1 M KOH, 1 M KCI as electrolytes, respectively are fabricated. Their capacitance from charge/discharge cycle tests are 0.34, 0.20, 0.10 Farad per centimeter squared per electrode, respectively. Their AC impedance curves are shown in Fig. 29. Device 5 has the highest capacitance and lowest ESR, but has the shortest cycle life. Device 7 has the lowest capacitance, but the longest cycle life. Leakage current curves in Fig. 30 reveal that the lower the capacitance, the lower the leakage current is observed as expected. Devices 5 and 6 survived less than 1 000 charge/discharge cycles. The capacitance of these devices drops as the ESR increases. Device 7 passed more than 10,000 charge/discharge cycles without any degradation after charging to 4.5 V as listed in Table 7. Table 7 Device 7 Charge/Discharge Data Cycles Charge Q Discharge Q Charge E Discharge E Charge t Discharge t (No.) (mAHr) (mAHr) (mWHr) (mWHr) (sec) (sec) 100 0.164 0.151 0.393 0.317 4.58 4.22 200 0.162 0.150 0.389 0.313 4.53 4.18 300 0.163 0.150 0.390 0.314 4.55 4.19 400 0.164 0.151 0.392 0.315 4.57 4.21 500 0.166 0.153 0.398 0.318 , 4.63 4.25 600 0.164 0.152 0.394 0.316 4.59 4.23 700 0.166 0.152 0.397 0.317 4.62 4.25 800 0.166 0.153 0.398 0.319 4.64 4.27 900 0.171 0.157 0.410 0.327 4.77 4.38 1000 0.171 0.157 0.41 1 0.327 4.77 4.38 From the CV curve shown in Fig. 30 the TiNO electrode material exhibits more than a 1 .0 V voltage window. It can be charged close to 0.20 V. Device 7 was used to test the maximum device voltage window. These data are listed in Table 8. As a comparison, a RuTaO x capacitor device having very good data is also included. Table 8 Device 7 Maximum Voltage * estimated data Figures 31 and 32 are the respective charge and energy curves of 1 000 charge/discharge cycles for Device 7 from 5.0V to 9.0V (from 1 .OV per cell to 1 .8V per cell) . Evaluating these curves and Table 8 the TiNO device using 1 .OM KCI as electrolyte can be safely charged to 1 .6V per cell. EXAMPLE 1 3 Five Cell — Data for three 5-cell TiNO packaged devices are shown in Table 9. Figure 33 shows the AC impedance data for these three devices. Fig. 34 reveals 1 8 hour leakage current data. Fig. 35 is the discharge energy and capacitance of these three devices for 5000 cycles at 5V. All devices using neutral electrolytes are very stable during the cycles. Of these, Device 8-4 shows the best electrical performance at low frequency. Table 9 Device Device 8-2 Device 8-3 Device 8-4 Electrode 1M KC1 1M KC1 1M LiCI Separator Cellulose Glass paper cellulose ESR 302 mΩ 142 mΩ 487 Ω Ω = ohm These three devices have been charged and discharged more than 1 V per cell for 5000 cycles on each voltage. Both coulomb and energy efficiencies are good. Among them, Device 8-4 shows the best performance. The capacitance data units are Farads per square centimeter per electrode. Additional properties are shown in Tables 1 0, 1 1 and 1 2. Table 10 Device No. 8-2 Discharge Data at 5000 Cycles Voltage V per cell Capacity Capacitance Efficiency Energy Energy Efficiency (V) (V) (mAHr) (F/cm 2 ) q ( ) (mWHr) (J) e (%) 5.0 1.0 0.10 0.056 94 0.23 0.83 85 6.0 1.2 0.13 0.060 92 0.37 1.3 80 7.0 1.4 0.16 0.064 91 0.53 1.9 77 8.0 1.6 0.20 0.070 90 0.71 2.6 73 Table 1 1 Device No. 8-3 Discharge Data at 5000 Cycles Voltage V per cell Capacity Capacitance Efficiency Energy Energy Efficiency (V) (V) (mAHr) (F/cm 2 ) q (%) (mWHr) (J) e (%) 5.0 1.0 0.066 0.037 92 0.16 0.58 84 6.0 1.2 0.089 0.041 90 0.25 0.90 78 7.0 1.4 0.11 0.044 89 0.36 1.3 75 8.0 1.6 0.13 0.045 88 0.47 1.7 73 Table 12 Device No. 8-4 Discharge Data at 5000 Cycles Voltage V per cell Capacity Capacitance Efficiency Energy Energy Efiiciency (V) (V) (mAHr) (F/cm 2 ) q (%) (mWHr) (J) e (%) 5.0 1.0 0.13 0.073 94 0.29 1.0 82 6.0 1.2 0.16 0.074 93 0.44 1.6 78 7.0 1.4 0.20 0.080 92 0.61 2.2 75 8.0 1.6 0.23 0.080 91 0.79 2.8 72 EXAMPLE 14 Storage devices No. 1 0-3 and 1 0-4 use 1 M LiCI as electrolyte, have a single gasket and a double gasket respectively. AC impedance curves are shown in Fig. 36. These two devices ESR are 0.27 and 1 .08 Ω respectively due to the different gaskets. The double gasket device has a higher performance also its ESR is higher too. The 60 min leakage current curves are shown in Fig. 37. The Maccor test equipment can only charge to maximum of 10 V. It is impossible to charge these devices to more than 1 V per cell. Single channel test equipment is used to perform charge and discharge device cycle test. The efficiencies are not very accurate, but can be used as a reference. The testing data is listed in Tables 1 3 and 1 4. After cycle testing at 1 7V, the ESR of device 1 0-3 and 1 0-4 increase to 0.39 and 1 .44 Ω. This also provides the evidence that the capacitor can not be charged more than 1 .6V per cell in neutral electrolytes. Table 13 Device No. 10-3 Discharge Data at 1000 Cycles Voltage V per cell Capacity Capacitance Efficiency Energy Efficiency (V) (V) (F) (F/cm 2 ) q (%) (J) E (%) 10.0 1.0 0.0273 0.042 99 1.15 82 11.0 1.1 0.0284 0.044 99 1.44 82 12.0 1.2 0.0284 0.044 97 1.69 78 13.0 1.3 0.0281 0.044 96 1.93 77 14.0 1.4 0.0288 0.045 98 2.24 76 15.0 1.5 0.0279 0.043 98 2.48 75 16.0 1.6 0.0273 0.042 97 2.75 74 17.0 1.7 0.0264 0.041 97 2.90 71 Table 14 Device No. 10-4 Discharge Data at 1000 Cycles Voltage V per cell Capacity Capacitance Efficiency Energy Efficiency (V) CV) (F) (F/cm 2 ) q (%) (J) e (%) 10.0 1.0 0.0402 0.062 100 1.76 84 11.0 1.1 0.0405 0.063 100 2.14 82 12.0 1.2 0.0405 0.063 96 2.53 79 13.0 1.3 0.0418 0.065 96 3.03 79 14.0 1.4 0.0436 0.068 100 3.65 81 15.0 1.5 0.0444 0.069 99 4.24 79 16.0 1.6 0.0446 0.069 98 4.79 77 17.0 1.7 0.0411 0.064 98 4.85 74 EXAMPLE 1 5 Physical Properties of potassium chloride pursuant to its use as a neutral electrolyte Aqueous Solubility - The solubility of KCI in water at ambient temperature was determined. Solutions of KCI were prepared starting at 1 .OM and ascending in 0.5M increments. The solubility limit was reached at 4.5 M where KCI precipitated out of solution upon cooling to ambient temperature. Freezing Point -- The freezing point of solutions of KCI as a function of molarity was determined. A small amount of solution was drawn into a capillary tube, then one end was sealed. The capillary tube was mounted onto a rod thermocouple which measured the temperature next to the solution in the capillary tube. This assembly was suspended in a stirred IPA isopropylalcohol (IPA) bath. Liquid nitrogen was added to the IPA to lower the temperature of the bath. Freezing was sudden, rapid, and easily seen. The bath temperature at which the KCI solution froze was recorded this procedure was repeated approximately 10 times for each molarity of solution. The third physical property to be measured was the conductivity of the above solutions. See Figure 36. The data suggests that the optimum concentration of Potassium Chloride as a neutral electrolyte is 3.0 M, or lies somewhere between 3.0M and 3.5M concentration in terms of both lower freezing point and higher conductivity. While only a few embodiments of the invention have been shown and described herein, it will become apparent to those skilled in the art that various modifications and changes can be made in the improved method to produce metal nitride or metal oxynitride coating for an electrode and/or using an aqueous alkali metal halide, such as KCI, as an electrolyte for use in an electrical storage device such as a battery or a capacitor having improved lifetime and charge/recharge characteristics and low leakage current, and the device thereof without departing from the spirit and scope of the present invention. All such modifications and changes coming within the scope of the appended claims are intended to be carried or thereby.

Claims: WE CLAIM: 1 . A process to produce a high surface area iron nitride, titanium nitride or gamma-molybdenum nitride coated substrate for use as an electrical energy storage component in a capacitor or a battery configuration, which process comprises: (a) coating one or both flat etched surfaces of a solid substrate, which substrate is in the form of a thin sheet, with a solution or a slurry of a metal halide selected from iron halide, titanium halide or molybdenum halide and a liquid volatile carrier to produce a thin surface film; (b) contacting the metal halide surface film-carrier coated substrate of step (a) with oxygen, air, or combinations thereof at a temperature of between about 1 50 and 400° C for between about 5 and 60 min to convert the iron halide, titanium halide or molybdenum halide to oxide, respectively, as a thin film and to remove the liquid volatile carrier; (c) repeating steps (a) and (b) as needed to obtain an accumulated thickness of metal oxide coating on the substrate, which accumulated metal oxide coating has a high surface area and the liquid volatile carrier is removed; (d) heating the metal oxide film coated substrate of step (c) in oxygen, air or combination thereof at between about 1 50 and 400°C for between about 1 and 3 hr to convert at least about 95% of the metal chloride to metal oxide; (e) slowly increasing the temperature of the metal oxide coated substrate at a rate of less than about 40°C per minute in a nitrogen atmosphere to between about 500 to 800°C; (f) contacting the oxide coated substrate produced in step (e) with a nitrogen source selected from excess flowing gaseous ammonia or a mixture of hydrogen gas and nitrogen gas at between about 500 and 800°C for between 1 and 6 hr which treatment converts about 95% or greater of the oxide coating to an iron nitride, titanium nitride or gamma-molybdenum nitride layer, respectively, on the substrate, which nitride layer has a high surface area and is electrically conductive; and (g) cooling to ambient temperature and recovering the high surface area nitride coated substrate produced in step (e). 2. The process of Claim 1 wherein the metal halide is selected from chloride or bromide. 3. The process of Claim 2 wherein in step (a) the metal halide is molybdenum chloride, and the gamma-molybdenum nitride film of step (f) has a surface area in excess of 1 6 m 2 /g. 4. The process of Claim 1 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper, zirconium, nickel or combinations thereof. 5. The process of Claim 1 wherein in step (b) the contacting occurs by dip coating or by stray coating. 6. The process of Claim 1 wherein the liquid volatile carrier is selected from ethanol, propanol, butanol, pentanol, hexanol, cycohexanol, diethyl ether, dioxane, tetrahydrofuran, dimethylacetamide, diethylacetamide, acetone, methylethyl ketone, butanone, ethyl acetate, propyl acetate, methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, xylene, or mixtures thereof. 7. The process of Claim 6 wherein the liquid volatile carrier is selected from ethanol, propanol, butanol, pentanol or hexanol. 8. The process of Claim 1 wherein: in step (a) the metal halide is molybdenum chloride, and the substrate is selected from titanium, molybdenum, iron, aluminum, copper or combinations thereof and the liquid volatile carrier is isopropanol; and in step (f) the nitrogen source is flowing ammonia, the temperature is between about 500 and 800°C for between about 1 and 6 hrs, and gamma molybdenum nitride is produced. 9. The process of Claim 8 wherein the surface area is between about 10 and 60 m 2 /g, and the temperature in steps (e) and (f) is about 700°C. 10. The process of Claim 6 wherein the carrier is the C 2 -C 6 alcohols, and water is present at less than 1 % by weight. 1 1 . The process of Claim 1 wherein: in step (a) the metal halide is titanium chloride and in step (f) titanium nitride is formed. 1 2. The process of Claim 1 1 wherein: in step (a) the liquid volatile carrier is isopropanol; in step (b) the temperature is between about 1 50 and 300°C and the time is between about 5 and 30 min.; in step (c) the number of repeating steps is between 1 0 and 20; in step (d) the temperature is between about 1 50 and 300°C and the time is between about 2 and 3 hr.; in step (e) the rate of heating is about 40°C per minute to 800°C; and in step (f) flowing gaseous ammonia with hydrogen is used at about 800°C for between about 3 and 5 hr. 1 3. The process of Claim 1 2 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper, zirconium, nickel or combinations thereof. 14. The process of Claim 1 1 wherein the liquid volatile carrier is an alcohol or a mixture of alcohols. 1 5. The process of Claim 1 wherein: in step (a) the metal halide is iron chloride and in step (f) iron nitride is formed. 1 6. The process of Claim 1 1 wherein: in step (a) the liquid volatile carrier is isopropanol; in step (b) the temperature is between about 1 50 and 300°C and the time is between about 5 and 30 min.; in step (c) the number of repeating steps is between 10 and 20; in step (d) the temperature is between about 1 50 and 400°C and the time is between about 2 and 3 hr.; in step (e) the rate of heating is about 40°C per minute to 500°C; and in step (f) flowing gaseous ammonia is used at about 500°C for between about 3 and 5 hr. 1 7. The process of Claim 1 5 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper or combinations thereof. 1 8. The electrically conducing molybdenum nitride coated electrode produced by the process of Claim 8. 1 9. The electrically conducting titanium nitride coated electrode produced by the process of Claim 1 1 . 20. The electrically conducting iron nitride coated electrode produced by the process of Claim 1 5. 21 . An electrical storage device which has as spaced electrodes of a metal sheet coated with a thin layer of a metal nitride selected from molybdenum nitride, titanium nitride or iron nitride. 22. A process to produce a high surface area niobium oxynitride, tantalum oxynitride, vanadium oxynitride, zirconium oxynitride, titanium oxynitride or molybdenum oxynitride coated substrate for use as an electrical energy storage component in a capacitor or a battery configuration, which process comprises: (a) coating one or both flat etched surfaces of a solid substrate, which substrate is in the form of a thin sheet, with a solution or a slurry of a metal halide selected from niobium halide, tantalum halide, vanadium halide, zirconium halide, titanium halide or molybdenum halide and a liquid volatile carrier to produce a thin surface film; (b) contacting the metal halide surface film-carrier coated substrate of step (a) with oxygen, air, or combinations thereof at a temperature of between about 1 50 and 250° C for between about 5 and 60 min to convert the metal halide to metal oxide, respectively, as a thin film and to remove the liquid volatile carrier; (c) repeating steps (a) and (b) as needed to obtain an accumulated thickness of metal oxide coating on the substrate, which accumulated metal oxide coating has a high surface area and the liquid volatile carrier is removed; (d) heating the metal oxide film coated substrate of step (c) in oxygen, air or combination thereof at between about 1 60 and 240°C for between about 1 and 3 hr to convert at least about 95 % of the metal chloride to metal oxide; (e) slowly increasing the temperature of the metal oxide coated substrate at a rate of less than about 40°C per minute in a nitrogen atmosphere to between about 500 to 800°C; (f) contacting the oxide coated substrate produced in step (e) with a nitrogen source selected from excess flowing gaseous ammonia, a mixture of ammonia gas and hydrogen gas, or a mixture of hydrogen gas and nitrogen gas at between about 500 and 800°C for between 1 and 6 hr which treatment converts about 95 % or greater of the oxide coating to an niobium oxynitride, tantalum oxynitride, vanadium oxynitride, zirconium oxynitride, titanium oxynitride or molybdenum oxynitride layer, respectively, on the substrate, which oxynitride layer has a high surface area and is electrically conductive; and (g) cooling to ambient temperature and recovering the high surface area metal oxynitride coated substrate produced in step (f). 23. The process of Claim 22 wherein the metal halide is selected from chloride or bromide. 24. The process of Claim 23 wherein in step (a) the metal halide is molybdenum chloride, and the molybdenum oxynitride film. 25. The process of Claim 22 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper, zirconium, nickel or combinations thereof. 26. The process of Claim 22 wherein in step (b) the contacting occurs by dip coating or by spray coating. 27. The process of Claim 22 wherein the liquid volatile carrier is selected from ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, diethyl ether, dioxane, tetrahydrofuran, dimethylacetamide, diethylacetamide, acetone, methylethyl ketone, butanone, ethyl acetate, propyl acetate, methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, xylene, or mixtures thereof. 28. The process of Claim 27 wherein the liquid volatile carrier is selected from ethanol, propanol, butanol, pentanol or hexanol. 29. The process of Claim 22 wherein: in step (a) the metal halide is molybdenum chloride, and the substrate is selected from titanium, molybdenum, iron, aluminum, copper or combinations thereof and the liquid volatile carrier is isopropanol; and in step (f) the nitrogen source is flowing ammonia, the temperature is between about 500 and 800°C for between about 1 and 6 hrs, and about 95 % to 100% of the molybdenum oxide is converted to molybdenum oxynitride. 30. The process of Claim 29 wherein the surface area is between about 10 and 60 m 2 /g, and the temperature in steps (e) and (f) is about 700°C. 31 . The process of Claim 27 wherein the carrier is the C 2 -C 6 alcohols, and water is present at less than 1 % by weight. 32. The process of Claim 22 wherein: in step (a) the metal halide is titanium chloride and in step (f ) titanium oxynitride is formed. 33. The process of Claim 32 wherein: in step (a) the liquid volatile carrier is isopropanol; in step (b) the temperature is between about 1 50 and 300°C and the time is between about 5 and 30 min.; in step (c) the number of repeating steps is between 10 and 40; in step (d) the temperature is between about 1 50 and 300°C and the time is between about 2 and 3 hr.; in step (e) the rate of heating is about 40°C per minute to 700°C; and in step (f) flowing gaseous ammonia with hydrogen is used at about 700°C for between about 3 and 5 hr. 34. The process of Claim 33 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper, zirconium, nickel or combinations thereof. 35. The process of Claim 32 wherein the liquid volatile carrier is an alcohol or a mixture of alcohols. 36. The process of Claim 22 wherein: in step (f) titanium oxynitride is formed having a BET specific surface area of between about 50 and 100 m 2 /g. 37. The process of Claim 22 wherein: in step (a) the liquid volatile carrier is isopropanol and the metal halide is selected from niobium chloride, tantalum chloride, vanadium chloride, or zirconium chloride; in step (b) the temperature is between about 1 50 and 300°C and the time is between about 5 and 30 min.; in step (c) the number of repeating steps is between 1 0 and 40; in step (d) the temperature is between about 1 50 and 400°C and the time is between about 2 and 3 hr.; in step (e) the rate of heating is about 40°C per minute to 800°C; and in step (f) flowing gaseous ammonia is used at about 800°C for between about 3 and 5 hr. 38. The process of Claim 36 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper or combinations thereof. 39. The electrically conducing molybdenum oxynitride coated electrode produced by the process of Claim 29. 40. The electrically conducting titanium oxynitride coated electrode produced by the process of Claim 32. 41 . The electrically conducting titanium oxynitride coated electrode produced by the process of Claim 24. 42. An electrical storage device which has as spaced electrodes of a metal sheet which coated with a thin layer of a metal oxynitride selected from molybdenum oxynitride or titanium oxynitride. 43. An electrode for use as a component in an electric energy storage device, which electrode comprises: an electrically conducting metal foil substrate which is coated on one or both flat sides with a high surface area metal oxynitride. 44. A high specific surface area electrode comprising an electrically conducting substrate and a film layer thereon on one or both flat surfaces wherein the film comprises an oxynitride of the metals of Groups III, IV, V, VI or VII of the Periodic Table. 45. The electrode of Claim 44 wherein the substrate is selected from iron, titanium, molybdenum, aluminum, copper, zirconium, nickel or combinations thereof; and the metal of the oxynitride is selected from niobium, titanium, tantalum, vanadium, zirconium or combinations thereof. 46. A process to improve the adhesion and cohesion of a high surface area metal nitride or metal oxynitride wherein the metal is independently selected from the metals of Groups III, IV, V, VI or VII of the Periodic Table, which process comprises: adding tantalum chloride or tantalum oxide to the metal nitride or metal oxynitride prior to drying, annealing or pyrolysis at elevated temperatures resulting in tantalum oxide in the product. 47. A double layer battery or capacitor device, which device comprises at least one cell having: (a) a high surface area adherent coating of a metal oxide, metal carbide, metal nitride, metal oxynitride or combinations thereof coated on an electrically conducting support (b) an opposing high surface area adherent coating of a metal oxide metal carbide, metal nitride, metal oxynitride or combinations thereof coated on an electrically conducting support; and (c) within the volume created between (a) and (b) a substantially neutral aqueous solution of an alkali metal halide. 48. The double layer battery or capacitor device of Claim 47 wherein: in (a) and (b) the coating is selected from the group consisting of a metal nitride, a metal oxynitride or combinations thereof. 49. The double layer battery or capacitor device of Claim 47 wherein: (c) the alkali metal halide is selected from the group consisting of NaCI, KCI, NaBr, and KBr. 50. The double layer capacitor of Claim 47 wherein the alkali metal halide is present in between 0.5 and 4.5 M. 51 . The capacitor device of Claim 47 wherein in (a) and (b) the coating is selected from high surface area metal nitride, metal oxynitride, or combinations thereof, and in (c) the alkali metal halide is KCI present in between about 1 .0 and 4.0M. 52. The capacitor device of Claim 51 wherein in (a) and (b) the metal portion of the nitride, oxynitride or combinations thereof is selected from iron, titanium, molybdenum, niobium, tantalum, vanadium, zirconium or combinations thereof. 53. The capacitor device of Claim 52 in (a) and (b) wherein the metal is titanium. 54. The double layer capacitor of Claim 53 wherein said capacitor is charged up to about 1 .6V and is stable to more than 5000 cycles of charging and discharging between 0 and 1 .6V.

Inventors: DENG CHARLES Z, GHANTOS DANIA, TSAI KEH-CHI, DENG, CHARLES, Z., GHANTOS, DANIA, TSAI, KEH-CHI
Applicants: DENG CHARLES Z, GHANTOS DANIA, PINNACLE RESEARCH INST INC, TSAI KEH CHI, DENG, CHARLES, Z., GHANTOS, DANIA, PINNACLE RESEARCH INSTITUTE, INC., TSAI, KEH-CHI
Application year: 1997
Main classification: H01G9
IPC codes: H01G9, H01M4