CA2267439A1 - High surface area metal nitrides or metal oxynitrides for electrical energy storage - Google Patents

High surface area metal nitrides or metal oxynitrides for electrical energy storage Download PDF

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CA2267439A1
CA2267439A1 CA002267439A CA2267439A CA2267439A1 CA 2267439 A1 CA2267439 A1 CA 2267439A1 CA 002267439 A CA002267439 A CA 002267439A CA 2267439 A CA2267439 A CA 2267439A CA 2267439 A1 CA2267439 A1 CA 2267439A1
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metal
oxynitride
molybdenum
titanium
nitride
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Charles Z. Deng
Keh-Chi Tsai
Dania Ghantos
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National Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

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, 1996 and is also a continuation-in-part of U.S. Serial No.
727,821, filed September 30, 1996, which is a continuation-in-part of U.S. Serial No.
219,965, filed March 30, 1994, which claims priority on U.S. Philippine Serial No. 93/5773, filed September 20, 1993 and which is also a continuation-in-part of U.S. Serial No.
947,414, filed September 18, 1992, now U.S. Patent 5,384,685, U.S. Serial No.
947,294, filed September 18, 1992, now U.S. Patent 5,464,453, and U.S. Serial No.
958,506, tiled October 7, 1992, now abandoned. It is also a continuation-in-part of and claims priority on PCT/US95/03985, filed March 30, 1995, which claims priority on U.S. Ser. No. 219,965, filed March 30, 1994 and U.S. Ser. No. 377,121, filed January 23, 1995. 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 Eneray 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 ( 1995) and R. Tong et al., United States Patent, 5,464,453 (1995)). 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. 5,055,169 issued October 8, 1991; H. Beer US
Patent no. 4,052,271 issued October 4, 1977; and A. Martinsons, et al. US
Patent no. 3,562,008 issued February 9, 1971. J. Wilfred in US Patent No. 4,774,193, issued September 27, 1988; and Maruyama et al in US Patent No. 4,764,181 issued August 16, 1988.
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 17 September 1993, Inventors: Tsai) K.C. et al., Int.
Pub. No.: WO 94/07272, Int. Pub. Date: 31 Mar 1994.
PCT/US95/03985, filed 30 March 1995, Inventors: Tsai, K.C. et al., Int. Pub.
No.: WO 95I26833, Int. Pub. Date: 12 Oct 1995.
PCT/US95/15994, filed 1 1 December 1995; Inventors: L.T. Thompson et al., Int. Pub. No. WO 96/19003, Int. Pub. Date: 20 June 1996.
Robert R. Tong, et al., U.S. Patent No.: 5,464,453, Issued: Nov. 7, 1995.
Robert Tong et al., U.S. Patent No.: 5,384,685, Issued: Jan. 24, 1995.
Additional U.S. Patents of general interest include 4,515,763; 4,851,206;
5,062,025; 5,079,674; 4,327,400; and 5,185,679.
Molybdenum Nitride (Mo2N, 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 (Mo031 with ammonia (NH3) is described to produce y-molybdenum nitride (MozN), which has a fcc structure with a surface area in excess 200 mz/g (L. Volpe and M.
Boudart, J. Solid State Chem., 59, 332 (198511.
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 12-14, 1994) 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, December4-6, 1995, Boca Raton, Florida describes the comparison of molybdenum nitrides formed by heating the molybdenum oxide film on the surface of a substrate with ammonia. MoClS may be used as a starting material. The product Mo2N is not pure and is contaminated with Mo02 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, 1995, 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, 1995, Boca Raton, Florida, in general that WO 98l14970 PCT/US97/17612 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. vo1.59, 332-347 (1985).
L. Volpe and Boudart M. "Ammonia synthesis on molybdenum nitride". J.
Phys. Chem, vo1.90, 4874-4877 (1986).
G.S. Ranhotra) et al.) "Catalysis over molybdenum carbides and nitrides ll.
Studies of CO hydrogenation and C2H6 hydrogenolysis". Journal of Catalysis.
vol.
108, 40-49 (1987).
G.S. Ranhotra, et al., "Catalysis over molybdenum carbides and nitrides I.
Catalyst characterization". Journal of Catalysis. vol. 108, 24-39 (1987).
E.J. Market and Van Zee, J.W. "Catalytic hydrodesulfuriza-tion by molybdenum nitride". Journal of Catalysis. vol. 126, 643-657 (1990).
C.H. Daggers, Michaels, J.N. and Stacey, A.M. "Preparation of high-surface area transition-metal nitrides: Mo2N and MoN. Chemistry of Materials. vol. 2, 157 (1990).
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 f 1992).
L.T. Thompson, Lolling, C.W., Choi, D., Demczyk, B.G. and Choi, J-G.
"Surface and catalytic properties of molybdenum nitrides". New Frontiers in Catalysis. 19-24 (1992).
Jeong-Gil Choi. "Temperature-programmed desorption of H2 from molybdenum nitride thin films". Applied Surface Science. vol. 78, 299-307 (19941.
R.S. Wise, and Market, E.J. "Catalytic NH3-decomposition by topotactic molybdenum oxides and nitrides: Effect on temperature programmed y-MOZN
Synthesis". Journal of Catalysis. vol. 145, 335-343 (19941.
K.L. Roberts and Market, E.J. "Generation of MOZN nanoparticles from topotactic M02N Crystallites". J. Phys. Chem. vol. 98, 4083-4086 (1994).
R.S. Wise and Market, E.J. "Synthesis of high surface area molybdenum nitride in mixtures of nitrogen and hydrogen". Journal of Catalysis. vol. 145, 355 (1994).
J-G. Choi, Curl, R.L. and Thompson, L.T. "Molybdenum nitride catalysts".
Journal of Catalysis. vol. 146, 218-227 ( 19941.

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 (1994).
E.P. Donovan and Hubler, G.K. "Ion-beam-assisted deposition of molybdenum 5 nitride films." Surface and Coatings Technology, vol. 66, 499-504 11994).
C.W. Lolling and Thompson, L.T. "The structure and function of supported molybdenum nitride hydrodenitrogenation catalysts". Journal of Catalysis. vol.
146, 193-203 ( 19941.
C. H. Daggers. "The preparation and characterization of high surface area transition metal nitrides". U. M. I. Dissertation Services. (1994).
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, 5138-5143 (1995).
H. Joon Lee, Choi, J-G, Coning, C.W., Mudholkar, M.S. and Thompson, L.T.
"Temperature-programmed desorption and decomposition of NH3 over molybdenum nitride films". Applied Surface Science. vol. 89, 121-130 (1995).
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. 140, 277-290 (1986).
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, 153-158 (1992).
E.O. Travis and Fiordalice, R.W. "Manufacturing aspects of low pressure chemical-vapor-deposited TiN barrier layers". Thin Solid Films. vol. 236, 325-119931.
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 ( 19951.
H. Rode, and Hlavacek, V. "Detailed kinetics of titanium nitride synthesis".
AIchE Journal. vol. 41, 377-388 ( 1995).
K-T. Rie, Gebauer, A., Wohle, 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 (1995?.
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 (19961.
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". lEEE Transactions on Magnetics. vof.
MAG-17, 3026-3031 ( 19811.
K. Tagawa, Kita E. and Tasaki, A. "Synthesis of fine Fe4N powder and its magnetic characteristics". vol. 21, 1596-1598 ( 1982).
M. Kopcewicz, Jagielski, J.) Gawlik, G. and Grabias, A. "Role of alloying elements in the stability of nitrides in nitrogen-implanted a-Fe". J. App/.
Phys. vol.
78, 1312-1321 (19951.
D.C. Sun, Lin, C., Jiang, E.Y. and Wu, S.W. "Multiphase iron nitride gradient films". Thin Solid Films. vol. 260, 1-3 ( 1995).
K.H. Jack. "The synthesis and characterization of bulk a"-Fe,6N2". Journal of Alloys and Compounds. vol. 222, 160-166 (1995).
T. Chuijo, Hiroe, K., Matsumura, Y., Uchida, H. and Uchida, H.H. "Reactivity of NZ with Fe in FeNx formation by activated reactive evaporation process".
Journal of Alloys and Compounds. vol. 222, 193-196 (19951.
F. Malengreau, 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 (1995).
None of these is art or in any configuration teaches or suggests the present invention.
Additional references of general interest include U.S. Patents 3,718,551;
4,816,356; 4,052,271; 5,055,169; 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 (TiNI 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 ( 1986) measured 3,um TiN film that had 8.5 Moh's hardness scale, on which diamond is 10. It has the resistivity of 55 ,u0 cm. Most of TiN thin films are produced by chemical vapor deposition (see, for example J.N. Musher et al. J. Electrochem Soc., vol. 143, p. 277 ( 19961, E.O. Travis, et al., Thin Solid Films, vol. 236, p.
325 ( 1993) and K.-T. Rie, et al., Surface and Coatin4 Tech., vol. 74-75, p. 375 ( 1995)1:
2TiCl4 + NZ + H2-~2TiN + 8HC1 900-1200 ~C
6TiCl4 + 8NH3-~6TiN + 24HC1 + Nz 500~C
Titanium Oxynitride (TiN0) 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. 136, p. 1 181,(19891) and/or a diffusion barrier fN. Kumar. et al. Thin Solid Films, vol. 153, p. 287 ( 1987)). Only gas nitriding of titanium dioxide (Ti0z1 produces high surface area titanium oxynitride f(C.H. Shin, et al., Journal Solid State Chemistry, vol.
95, p. 145 (1991 )). H. Teraoka, et al., in Japanese Patent 89 - 60729 describe that the titanium oxynitride is obtained by the reduction of Ti02 in nitrogen atmosphere.
Additional references for TiNO include:
C.H. Shin, et al., Journal of Solid State Chemistry, vol. 95, 145-155 ( 19911 disclose the preparation and characterization of titanium oxynitride having high specific surface area.
R. Marchand, et al., U.S. Patent 4,964,016 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 I19871 disclose the nitridation of Ti02 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;
(bl contacting the metal halide surface film-carrier coated substrate of step (al with oxygen, air, or combinations thereof at a temperature of between about 150 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 (b1 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;
(dl heating the metal oxide film coated substrate of step (c) in oxygen, air or combination thereof at between about 150 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 ff) has a surface area in excess of m2/g.
in another embodiment, in step (g) the metal nitride formed on the substrate has a surface area of between about 10 and 60 m2/g, and a specific capacitance up to about 130 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 150 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 fb) 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 150 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 5 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 10 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.

WO 98/14970 PCT/US97/i7612 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., TiN01 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 tong-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 Mo2N
film.
Figure 3 is a graphic representation of cyclic voltammetry of Mo2N 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/cm2 and specific capacitance in versus BET specific surface area in mz/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 120 CV cycles (16 hrs) in 1 molar KOH, and Figure 7C is after 120 hrs CV cycles ( 16 hrs) in 3.5M sulfuric acid.
Figures 8A, 8B and 8C are scanning electron micrographs at 1000 magnification of the titanium oxynitride as a fresh sample, after 120 CV cycle in 1 M
KOH and after 120 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 RuTaOx, respectively.
Figures 10A, 10B and 10C show scanning electron micrographs at 200 magnification of TiNO with 0%Mn, 5% Mn and 10% Mn, respectively.
Figure 11 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 12 is a graphic representation for the leakage current test in 1 M
potassium hydroxide for TiNO for leakage current density in NA/cmz versus time in hours.
Figures 13A, 13B and 13C are scanning electron micrographs of TiNO for a fresh sample ( 13A) and after EDM cut, wash and dry ( 13B and 13C), respectively.
Figures 14A and 14B are scanning electron micrographs at 1000 magnification of TiNO and TiNO plus TiOz, respectively.
Figure 15 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 16 is a graphic representation of the TiNO stability test of capacitance in F/cmz versus cycles for CV materials, single cell device and for a five cell device.
Figures 17A and 17B are scanning electronic micrographs at 250 magnification showing crack structure of TiNO and RuTaOx, respectively.
Figure 18 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 19 is a graphic representation of an aqueous 1.0M LiCI single cell clamped test sample showing the same variables as described in Figure 18.
Figure 20 is a graphic representation of a single cell test sample in aqueous 1.0M LiCI and in 1.0 M KOH for an 18 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, 1.0M KCI, 1.0M
KCI
(with a glass separator, and 1.0M 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 t500-50001. The electrolytes are aqueous solutions of 1.0M LiCI 1 .OM
KOH, 6.0M KOH, 1.OM KCI, 1.0M KCI (with a glass separator) and 1.0M CsCI.
Figure 23 is a graphic representation of TiNOx electrodes AC impedance data which plots real impedance (in ohms) versus frequency (Hz). Capacitance in Farads is also plotted. The aqueous solutions include 1.0M KOH, 6.0M KOH, 1.0M KCI
(cap), 1.0M KCl gls, 1.0M LiCI; 1.0M CsCI, 1.0M, CsCI (real), 1.0M KCI (real), 1.0M
KCI gls (real) 1.0M KCI (real), 6.0M KOH (real), and 1.0M (real).
Figure 24 is a graphic representation of TiNO electrodes for an 18 hour leakage current test for a single cell device clamped sample in various electrolytes leakage current (,uA1 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 (Hzl.
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 (,u A/cm2) 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 1.0M KCI at various charging voltages. which plots charge (m A Hour) versus cycles (0 to 1000).
Figure 34 is a graphic representation of a 5-cell TiNO device in 1.0M 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 f Hzl. Capacitance in Farads is also plotted.
Figure 36 is a graphic representation of the test of three 5-cell devices which plots current density (NA/cm2) 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 1.0M KCi at 10.0V plotting leakage current in NA
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, W094/07272 and W095/26833 are incorporated herein in their entirety.

WO 98l14970 PCT/US97117612 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 5 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 10 been cleaned as described in U.S. Patent 5,464,453, or by contact with a 6N
HCI
solution for 10-15 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 15 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.

WO 98/14970 PCTlUS97117612 "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 M02, M03, M04) etc. with MN, M2N, M3N, MNz etc. MNO describes a general formula MxNYOZ wherein M is metal, preferably a transition metal wherein:
x is between 0.7 and 7 .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 Ti02, and TiN, or variations thereof. TiNO is a general formula Tix NY OZ 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 Eneray Storage Device Referring now to the drawings, and more particularly to Figure 1 thereof, there is illustrated a dry preunit of energy storage device 10 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 12 and 1 i 4, 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 110, 112 and 114. The cells have generally similar design and construction, and therefore, only the cells 114 and 112 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 121 and 123.
When the first and second electrodes 1 1 1 A and 1 1 1 B, and the insulating gaskets 121 and 123 and the electrically conducting porous material (oxide) layers 1 19 and 120 are bonded together to form the cell 1 14, a central air filled gap is formed by these elements. When the preunit 10 is ready to be used, the gap 130 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 121 and 123, in order to allow the electrolyte to fill the gap. The fill port is formed by means of a tab or cord 1 17A, which is inserted between the gaskets and 123, prior to fusing or bonding the gaskets 121 and 123. When the gaskets 121 and 123 are heated, the cord 1 17A 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 19 and 120.
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.
Mo2N -- The molybdenum nitride (Mo2N) and molybdenum carbide (Mo2C) ceramic electrodes are both- excellent embodiments for an ultracapacitor. Both ceramics are electronically conductive, have very high specific surface area (e.g. >
100 mz/g), e.g. between 50 and 250 mz/g, have mechanical, stability and chemical stability as well as electrochemical stable in aqueous and nonaqueous electrolytes.
Mo2N electrodes are prepared by first spray pyrolysis or dip coating pyrolytic hydrolysis of (MoClS + 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. Mo03 and Mo02. The high surface area ceramic oxides are then converted to MoZN by reacting Mo03 or Mo02 with ammonia, NH3, 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 NH3, a mixture of N2 + HZ 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, Mo2C -- When carbon mono-oxide, CO, is substituted for NH3, 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 18 is that the electrode 1 1 1 A optionally includes a tab 160A, 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 19, which is deposited on a support material or structure 1 16, while the bipolar electrode 1 1 1 B includes two porous coating layers 120 and 131, which are deposited on either or both sides of the support material or structure 1 18.
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 16 and 1 18. 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 116 is generally thicker than the support material 1 18. In the preferred embodiment, the support material 1 16 has a thickness of about 10 mils (0.0254 cml, while the support material 1 18 has a thickness of about 1 mil (0.00254 cml. 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 119 and 120 in greater detail, the methods of forming them are described below. In the preferred embodiment, the coating layer 1 19 includes a plurality of microprotrusions, while the coating layer 120 does not include such microprotrusions. It should be understood, however) that the coating layer 120 could alternatively be designed similarly to the coating layer 1 19, without departing from the scope of the invention.
Considering now the coating layer 120, it serves a similar function as the coating layer 1 19, 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 120 does not include microprotrusions. In an alternative embodiment of the preunit 10, the coating layers 1 19 and 120 are similarly constructed, and include microprotrusion layers.
Considering now the gaskets 121 and 123, the methods of producing them will be described later. The gaskets 121 and 123 are generally identical, and are 5 arranged in registration (adjacent and superposable) with each other. For brevity, only the gasket 121 will be described in greater detail. The gasket 121 includes a solid peripheral section and a hollow central section.
In the preferred embodiment, the cord 117A, or a part thereof, is placed between the gaskets 121 and 123, and extends across the hollow section, of the 10 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 15 Referring to Figure 1, a general description for the preferred method to produce the dry pre-unit 10 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 N, preferably between about 1 and 200 ,u, and more preferably between about 5 and 50 N.
20 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 ( 1977).
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 cm2 of the interfacial surface area fi.e. the BET surface area), then surface enhancement capacitance densities of about 0.1 to 10 farads/cm2 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 10 and 1000 m2/cc are preferred, and preferred values between about 20 and 200 mz/cc, more preferably about 100 m2/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/cm2 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 0-150 ~ 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 150 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 tort 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 (VII species and/ or combinations thereof at temperatures between about ambient to 100 ~ C for 0.1-6 hr. A
preferred procedure uses a 10-100 mg/I 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 (HI 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 Tm 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, N21. 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 tort to 1 microtorr, preferably about 250 mtorr to less than 1 tort, 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 reflow and a fill port is not required.
The electrode capacitance density fC' in units of F/cmz) is roughly 1 F/cmz for every 10 ,um 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 cmz) divided by two times the number of cells (n) (equation 1 ).
The leakage current li") 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 NA/cm2.
The total number of cells in a device In) 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 (hl, 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 51.
eqn. 1 C = C'A'/2n 5 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 10 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 1000 V) large energy ( 1-5 F/cm2) storage device is used with an electrode area of about 100 to 10,000 cm2.
15 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 12 to 50 V constructed with around 100 to 1000 cm2 area electrodes of 1-5 F/cm2.
Optionally, a device consisting of several devices in parallel can be constructed to meet the electrical requirements.
20 For defibrillator applications about a 200-400 V device with 0.5 to 10 cmz area electrodes of 1-3 F/cm2 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.
25 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 150-400~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 ,u). The coated sheet is then annealed at 150 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 ,u, preferably (5-100 micron).
Generally, the maximum temperature for the Mo2N production is about 700~C, the temperature for the TiN production is about 800~C, and the temperature for FexN
production (where x = 2, 3 or 4) is about 500-550~C.
Titanium Nitride -- 1 M Titanium chloride (TiCl4) 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/cmz 23 F/g, about 30 mz/g (BET) in surface area.
Iron Nitride -- 1 M iron chloride FeCl3, optionally with FeCl2 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/cmz~ 75 F/g, and 30 m2/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. tt matches to the Joint Committee on Powder Diffraction Standards (JCPDS) computer data base of fcc y-Mo2N structure.
Typical cyclic voltammetry (CV) test results of Mo2N in 3.5M H2S04 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/cmz, 125 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 Mo2N 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 16 m2/g for the Mo2N 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 TiCl4 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 150~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 NH3 flowing (22.5 L/min) and H2, t4.5 L/min flowing) gas atmosphere at 700~C at ambient pressure, the TiNO is produced.
TiNO
shows the BET specific surface area of 56 m2/g and the highest capacitance up to 1.51 F/cm2, 79 F/g in 3.5M HZS04 and 1.45 F/cm2, 75 F/g in 1.0M KOH with a 1.2 voltage window from CV curves (see Figure 41. 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).

ESCA analysis of TiNO
Element Ti O N C Ar Atomic 30 35 21 13 1 ' Percent Rutherford Backscatering Spectroscopy (RBS) Analysis and SEM Micrographs WO 98/14970 PCTlUS97117612 The RBS result (Table 2) is consistent with the ESCA result for TiNO samples.
The ratios of Ti:O: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, O 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.

RBS result of TiNO samples in atomic percentage CapacitanceS.C. Surface Ti O N
(F/cm2) (F/g) Area (%) (%) (%) (m2/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/cm2 in 1 M KOH, after 120 continuous CV cycles ( 16 hrs) the capacitance decreased to 0.80 F/cm2 in 1 M
KOH, while the decrease was to 0.16 F/cm2 in 3.5M HZSOA. 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 120 CV cycles in both acid solution (Figure 7B) and alkaline solution (Figure 7C). The peaks of fresh sample and the sample after 120 CV cycles in KOH
solution show the peak position in between Ti0 and TiN. The sample after 120 CV cycles in 3.5M HZS04 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 120 CV cycles (16 hours) in alkaline solution (Figure 22B) and acid solution (Figure 22C). The morphologies are the same of the fresh sample and the sample after CV cycles in KOH. The sample after 120 CV cycles in 3.5M HZS04 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 HZS04.
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 HZS04 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 180 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 RuTaOX.
Zirconium and Manganese as Cementation Materials The samples of 15% 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 TiC14 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 16 m2/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~, which yields a specific capacitance of 46 t 4 F/g. The average capacitance of TiNO + 1 %Mn is 0.63 t 0.05 F/cmz, which yields the specific capacitance of 47 ~ 4 F/g.
Both materials have relative errors of 8%, or deviation of 7%. These errors 5 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 faund in Table 3.

Capacitance of TiNO and TiNO + 1 % Mn 10 No SheetSample Capac~itan~ce_ Surface Area (Flcmj) (miJ~) f~OR ~~ _ 0.60 4 l ( 19 I TiN(~
-6();i B TiN()+1 ~/~.I~ln0.65 ~ 'i6 !

<,ORL~ ~ TiNO ().4f~ I 35 ~ I

6f1821 B' TiNO+i!'~.~ln(1.27 35 I Fault 6R22 B TiNn 0.55 38 ( 15 6Ok23 ,a' TiNn+1 ~l"Mn n/a 37 Fault G0835 I TiNU+l~lat~-in0.61 ~ 36 B' G()b2f~I TiNU c).55 1 37 .a ~,clK?7.a TiN() ().f~a 37 ~ox2x ! TiNC )+ I c).5:~ I 35 .a' ~i~Mn B' TiNf)+t'a t).h~) 3~) Mn 20 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, TaClS is not economical in the TiNO system and replacement materials such as MnCl2 and ZrCl4 25 were investigated.
Incorporation of MnClz and ZrCl4 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 Ti02. The 30 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% MnCl2 to the 1 M TiCl4/IPA solution improved the adhesion of the coating but lowered the surface area. (Se Figures 24A, 24B and 24C). The more MnCl2 was added to the solution, the lower the surface area became. Therefore only a limited amount ( <5%) of MnClz was added to the system.
The advantage of using MnClz over ZrCla is that all phases of Mn02 are conductive unlike Zr02 where its presence can lower the capacitance of TiNO.
Different amounts of ZrCl4 were added to the precursor solution of ( 1 M
TiCl4/IPA) to further improve adhesion. The amount of the additive varied from to 65 %. The adhesion was very good for up to 35 % ) but flaking was observed in the electrodes with the higher ZrCl4 content. The surface of the electrodes was very smooth while the specific surface area increased with increasing ZrCl4 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 ZrCl4 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 Ti02 film using the 1 M TiCl4/IPA
solution on a Ti substrate with 15 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 10 min. vamping (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 m2/g vs.

m2/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 TiOz. Using the 1 M TiCl4/IPA on 5 mil Ti with 15 coats at 20Q~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 10 minutes (in between each coat onlyl. After adding 15 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 Ti02 electrode process in three different methods at the same conditions (1 M TiCl4/IPA; 5 mil Ti; 15 coats; 200~C; 2 hour anneal) are:
standard coating process 36 mz/g reactor w/out steam 25 m2/g reactor w/steam 90 m2/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/cm2l. A11 results have been reproducible at different conditions.
Nitriding Ramping Rate and Reaction Temperature.
Temperature programmed reaction is a slow increasing Cramping) rate in order to produce the maximum surface area. Different vamping 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 vamping 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:O
ratio of 4:1. The sample color is close to gold. The capacitance is 23 F/cm2 (BET
surface area 26 m2/g), about half the capacitance and half the surface area compared to nitriding at 700~C (0.54 F/cm2) 59 m2/g).
The relation of tamping rate and capacitance Ramp Rate 0 1.9 3.5 7.0 14.0 (hr) Reaction 4 4 4 4 4 Time (hrs) Capacitance0.32 0.42 0.54 0.50 0.55 (F/cm2) 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 f2 cmz). 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 RuTaOX film in acid.
Both of them are about 0.4F1 in single test tubes.
The leakage current test is carried out that two pieces of TiNO which are cut to about 4 cm2 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 ( 1.32) 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.

Leakage current test in 1 M KOH
Voltage Electrode CapacitanceLeakage Current at 30 (V) (F/cmz) min.
(NA/cm2) 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 15 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 12.9 cm2 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/cmz.
After EDM cut the material it is washed in 1 M KOH and DI water, and has a capacitance of anly 0.3 F/cm2. 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/cm2 per electrode.
The first TiNO five-cell ultracapacitors last several hundred cycles. The ESR
starts at 200 MS2, then increases to several kit.
The XRD shows oxide patterns on some sides of electrode sheets. The BET
specific surface area of electrodes are: original 43 m2/g, both sides TiNO 46 m2/g) and one side TiOz one side, TiNO 31 m2/g. The SEM pictures clearly show that when TiOz ball cluster involved, the TiNO structure disappeared. (Figure 14A and 14B).
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 + 2H20 + e' -~ TiOz + NH3 + OH' (4?
The second packaging material for 12.9 cm2 has a 1.0 F/cmz 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 15. The charge current is vary from 99 mA to 800 mA which corresponds to the discharge time vary from to 0.3 seconds. The energy density and power density are calculated using active material weight only.
30 Substantially Neutral Aaueous 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 5 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.
10 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 15 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.
20 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 1(e.g. nitride and/or 25 oxynitride) is porous and composed of mosly micropores (diameter < 171.
Large 0.1-1Nm 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 a micropores. The average diameter of these micropores are around 6-12 A. In a addition the micropores, a narrow distribution of mesopores (diameter < 17-1000A) a 30 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.

Molvdenum Nitride and Titanium Oxvnitride Material Stabilitv Test Two TiNO materials have been used for packing ultracapacitor devices. One has capacitance of 0.8 F/cm2 while the other has 0.2 F/cm2. 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 RuTaOX 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 mz/g) preferably about 20 to 56 m2/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 (FeCl3) or (FeCl2) are also obtained from Alfa Aesar and are essentially free of water.

METAL NITRIDE
(a) A solution Ior slurry) of MoClS 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 Mo03 and Mo02 are formed. The sheet is coated, dried and heated several times to obtain the desired thickness of Mo03 and Mo02. Optionally, the w 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 Mo2N 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 NZ and H2, the corresponding useful Mo2N electrode and energy storage device is obtained.

METAL CARBIDE
(a) A solution (or slurry) of MoClS 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 Mo03 and Mo02 are formed. The sheet is coated, dried and heated several times to obtain the desired thickness of Mo03 and MoOz. 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 Mo2C 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.

Molybdenum Nitride Mo2N - 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 150-400~ C for between about 5 and 60 minutes. The dip coating and oxidation and removal of isopropanol is repeated for 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 NH3 gas (13 i/min) over the oxide sheets at a temperature of about 700~ C.
This 15 molybdenum nitride material is characterized by XRD, SEM, EDAX and AES. The ultracapacitor performance of Mo2N material is evaluated by cyclic voltammetry (CV), package cell charge-discharge cycles and leakage current measurement using KOH
and HZS04. .

Molybdenum Nitride (with Tantalum Oxide) Molybdenum chloride and Tantalum chloride TaCS (1:1 atomic ratio) are combined in isopropanol. The procedure of Example 1 is then repeated. The MoZN/TaOx 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.

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 15 times until the desired level of coating on the foil. The fiirn 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 I/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 I/min) is combined with the ammonia at greater than 800 ~ C for 4 hrs. The resulting metal nitride has similar properties.

Iron Nitride A titanium substrate foil was coated with 0.7 M ferrous chloride-ferric chloride (FeCl2 + FeCl3) solution of isopropanol. The sheets were dip coated 15 times and dried in a reactor at 75~C for 10 min then pyrolysis at 200~C for 10 min.
The coated substrate is then heated up to 500~C. The substrate is contacted with ammonia gas (flowing) 110-20 L/min) at 500 ~ C for 4 hr. The FexN where x is 2,3,4 films produced is determined by XRD. The FexN coating has good adherence to the substrate. In an electrode configuration with 1 M KOH, it has a specific capacitance of 30 F/g.

Molybdenum Oxynitride (a) Mo2N0 - 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 (yenta) chloride in isopropanol film is first converted to molybdenum oxide in an oven by pyrolysis at temperatures between about 150-400 ~ C for between about 5 and 60 minutes. The dip coating and oxidation and removal of isopropanol is repeated for 15 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 NH3 gas (13 I/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 MozNO material is evaluated by cyclic voltammetry (CV), package cell charge-discharge cycles and leakage current measurement using KOH and HZS04.

(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 5 chloride is replaced with a stofchiometrically 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.
10 (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(a1 is repeated except that the molybdenum chloride is replaced with a stoichiometrically equivalent amount of zirconium chloride 15 a corresponding amount of zirconium oxynitride is obtained.

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 20 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 15 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 25 flowing ammonia ( 10-20 I/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 30 tetrachloride is replaced with a stoichiometrically equivalent amount of niobium chloride a corresponding amount of niobium oxynitride is obtained.
(c) Similarly, when Example 81a) 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 81a) 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 8fa) is repeated except that hydrogen gas (1-5 I/min) is combined with the ammonia at 700 ~ C for 4 hrs. The resulting metal oxynitride has similar properties.

Use of Neutral Electrolyte, LiCI
(CV Capacitance 0.39 F/cmz, 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 cm2 size. Comparing Figure 18 to Figure 19 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 18 and 19.
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 Electrol a LiCI KOH

C in (F 0.I5 0.43 C out F 0.13 0.37 El~cienc % 84 8b Ce in 0.17 0.49 Ce out 0.11 0.29 Ef~cienc a % 67 59 WO 98/14970 PCTlUS97/17612 Comparison of Hydroxide and Chloride Electrolytes (CV Capacitance 0.25 F/cm2, 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 cm2 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 ace 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 v~rhen compared to alkaline electrolytes. In neutral electrolytes, the ESR
decreased after a series test. This series includes: AC impedance test, a 18 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 12.9 cm2) 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 RuTaOx ultracapacitor.

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 10,000 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 180 mohm.
Unfortunately, this device can not be charged to 0.5V.

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 1000 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.

WO 98l14970 PCTlUS97/17612 Table 7 Device 7 Charae/Dischar4e Data CyclesCharge Discharge Charge Discharge Charge Discharge (~lo.)Q Q E E t t (mAHr) (mAHr) (mWHr) , (mWHr) (sec) (sec) 100 0.164 0.1S1 0.393 0.317 4.S8 4.22 200 0.162 0.1S0 0.389 0.3l3 4.53 4.l8 300 0.163 0.1S0 0.390 0.314 4.SS 4.19 400 0.164 0.1S1 0.392 0.31S 4.57 4.21 S00 0.166 0.1S3 0.398 0.318 4.63 4.2S

600 0.164 0.1S2 0.394 0.316 4.S9 4.23 700 0.166 0.1S2 0.397 0.3I7 4.62 4.2S
~

800 0.166 0.1S3 0.398 0.319 4.64 4.27 900 0.l71 0.1S7 0.41G 0.327 4.77 4.38 1000 0.I71 0.257 ~ 0.411 0.327 ( l4.77 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 RuTaOX capacitor device having very good data is also included.
Table 8 Device 7 Maximum Voltacte Electrode TiI~O TiNO TiNO TiNO TiNO RuTaOx ~

Electrolyte 1 M KCl 1 M KCl 1M KCl 1 M KCl 1 M KCl 4.6M
HzSO, Device S cell S cell S cell S cell S cell 10 cell Size (cm ~ 12.9 12.9 12.9 12.9 l2.9 12.9 Charge V (V) S 6 7 8 9 9 26 Charee (mAHr) 0.19 0.26 0.31 0.39 0.46 1.60 Dischar~e (mAHr) 0.18 0.24 0.29 0.36 0.42 1.SS

Efficiency (%) 92.6 91.7 91.9 91.9 90.S 96.9*

Discharge C (F/cm0.100 0.112 0. I 0.126 0.130 0.961 ) 16 Charge E (mWHr) 0.S2 0.83 1.2 1.7 2.2 7.S

Discharge E (mWHr)0.42 0.6S 0.91 1.3 1.6 6.2*

Discharge E (J) 1.S 2.3 3.3 4.7 S.8 22.3*

gfficiencv a (rb)80.6 77.9 77.S 76.2 71.5 82.9*

Discharge t (sec)S.0 6.7 8.1 10.1 11.7 48 Discharge P (W) 0.30 0.34 0.41 0.47 0.S0 0.46*
~

C after 1000 cyclesstable Stable stable stable Decreas stable a ESR after 1000 389 ~ 383 ~ 383 363 400 ~ 3S
cycles ~ ~
(ms2 ) 1..J~L110K.11 (lQZa Figures 31 and 32 are the respective charge and energy curves of 1000 charge/discharge cycles for Device 7 from 5.0V to 9.0V (from 1.0V 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.

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 18 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 10 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 KCl 1M KCl 1M LiCI

Sevarator Cellulose Glass a er cellulose ESR 302 m.S~, 142 mS'2 487 mS2 fl = ohm These three devices have been charged and discharged more than 1 V per cell 20 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 10, 11 and 12.
Table 10 25 Device No. 8-2 Discharge Data at 5000 Cycles VoltageV per Capacity CapacitanceEfficiencyEnergy Energy Efficiency (V) cell (mAHr) (F/crn2) (%) (mWHr) (.n a (%) (V) 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 80 307.0 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 11 Device No. 8-3 Discharge Data at 5000 Cycles VoltageV per Capacity CapacitanceEfficiencyEnergy Energy Efficiency (V) cell (m~) (Flcmi) (%) (m~) (I) a (%) (V) 5.0 1.0 0.066 d.03? 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 VoltageV per CapacityCapacitanceEfficiencyEnergy Energy Efficiency (V) cell (mAHr) (F/cm2) (%) (mWHr) (I) a (%) (V) 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.b1 2.2 75 208.0 i.6 0.23 0.080 91 0.79 2.8 ?2 Storage devices No. 10-3 and 10-4 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 f2 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 13 and 14. After cycle testing at 17V) the ESR of device 10-3 and 10-4 increase to 0.39 and 1.44 f2. 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 VoltageV per CapacityCapacit EfficiencyEnergyEfficiency (V) cell (F7 2nce (%a) (17 E (%) (V) (F~cm ) 10.0 1.0 0.0Z73 0.042 99 I.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 0.0d 1 97 2.90 71 Table 14 Device No. 10-4 Discharge Data at 1000 Cycles VoltageV per Capacity CapacitanceEfficiencyEnergy Efficiency (V) cell (~ (F/cmz) (%a) (n (V) 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 1S.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 Physica! Proaerties of potassium chloride~~ursuant to its use as a neutral electrolyte Aaueous Solubility -- The solubility of KCI in water at ambient temperature was determined. Solutions of KCI were prepared starting at 1.0M and ascending in 0.5M increments. The solubility limit was reached at 4.5 M where KCl precipitated out of solution upon cooling to ambient temperature.
Freezin~~ 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 KCl 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 IoW 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 (54)

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 150 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 voiatiie carrier is removed;
(d) heating the metal oxide film coated substrate of step (c) in oxygen, air or combination thereof at between about 150 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 16 m2/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 m2/g, and the temperature in steps (e) and (f) is about 700°C.
10. The process of Claim 6 wherein the carrier is the C2-C6 alcohols, and water is present at less than 1 % by weight.
11. The process of Claim 1 wherein:
in step (a) the metal halide is titanium chloride and in step (f) titanium nitride is formed.
12. The process of Claim 11 wherein:
in step (a) the liquid volatile carrier is isopropanol;
in step (b) the temperature is between about 150 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 150 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.
13. The process of Claim 12 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper, zirconium. nickel or combinations thereof.
14. The process of Claim 11 wherein the liquid volatile carrier is an alcohol or a mixture of alcohols.
15. The process of Claim 1 wherein:
in step (a) the metal halide is iron chloride and in step (f) iron nitride is formed.
16. The process of Claim 11 wherein:
in step (a) the liquid volatile carrier is isopropanol;
in step (b) the temperature is between about 150 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 150 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.
17. The process of Claim 15 wherein the substrate in step (a) is selected from iron, titanium, molybdenum, aluminum, copper or combinations thereof.
18. The electrically conducing molybdenum nitride coated electrode produced by the process of Claim 8.
19. The electrically conducting titanium nitride coated electrode produced by the process of Claim 11.
20. The electrically conducting iron nitride coated electrode produced by the process of Claim 15.
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 150 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 160 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 m2/g, and the temperature in steps (e) and (f) is about 700°C.
31. The process of Claim 27 wherein the carrier is the C2-C6 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 150 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 150 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 m2/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 150 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 150 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.
CA002267439A 1996-09-30 1997-09-30 High surface area metal nitrides or metal oxynitrides for electrical energy storage Abandoned CA2267439A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US72782196A 1996-09-30 1996-09-30
US08/727,821 1996-09-30
US08/761,837 1996-12-09
US08/761,837 US5980977A (en) 1996-12-09 1996-12-09 Method of producing high surface area metal oxynitrides as substrates in electrical energy storage
PCT/US1997/017612 WO1998014970A1 (en) 1996-09-30 1997-09-30 High surface area metal nitrides or metal oxynitrides for electrical energy storage

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