CA2233337A1 - Electrical energy devices using conductive ceramic fibers - Google Patents

Abstract

The performance of electrochemical energy devices such as batteries, fuel cells, capacitors and sensors is enhanced by the incorporation of ceramic materials in the form of fibers, powder, chips and substrates. Preferred are fibers having a length varying from about 10 to about 10,000 microns. The fibers may also be coated with metal.

Description

CA 02233337 l998-03-27 WO 97/12410 PCTrUS96/15621 Electrical Ener~y Devices Using Conductive Ceramic Fibers Priority is claimed to provisional application 60/004553, ~iled September 29, 1995.

TECHNICAL FIE~D
The present invention relates to electrochemical devices such as batteries, ~uel cells, capacitors and sensors which employ electrically conductive ceramic materials, ~ibers, powder, chips and substrates therein to improve the per~ormance o~ the electrochemical device.

R~CKGROUND ART
There are numerous applications which involve the trans~er o~ electrical current in environments which are highly corrosive or otherwise degrading to metallic conductors. Most notably are electrochemical devices operating under highly corrosive conditions and high temperatures. Examples o~ such applications are the use o~
electrodes ~or the chlor-alkali cell to make chlorine gas, electrodes ~or metal recovery, electrodes in hydrogen/oxygen ~uel cells, electrodes ~or producing ozone, electrolysis o~
water and electrodes in high temperature solid oxide ~uel cells. Most o~ these applications involve the contact o~ an electrode with an electrolyte under conditions which render the electrode i~e~ective during prolonged use The loss o~
e~iectiveness can be gradual, such loss being mani~ested by reduced current-carrying capacity of the electrode. Exemplary types o~ conditions which render electrodes ine~ective as they are used in current-carrying applications are described below.
One such condition involves chemical attack o~ the electrode by corrosive gas which is evolved ~rom the electrolyte as it is decomposed during use. For example, the evolution o~ chlorine gas, a highly corrosive material, ~rom CA 02233337 l998-03-27 an aqueous chloride-containing electrolyte such as, in the chlor-alkali cell is exemplary.
Another type o~ condition involves passivation of the electrode as it combines with the anions from the electrolyte to ~orm an insoluble layer on its surface. This passivation condition occurs when the product from the electrochemical reaction can not dif~use from the electrode surface and this produces a bloc~ing of the electrochemical sites and/or pores.
The end result is a ~im;ni shing of the electrode current carrying capacity. An example of this passivation is the lead dioxide electrode in an aqueous sulfuric acid solution.
Another type of condition which renders electrodes inef~ective involves the dissolution of the electrode by the electrolyte. The use of a zinc electrode in an aqueous potassium hydroxide solution is exemplary.
Various types of batteries such as secondary(rechargeable) batteries: lead-acid(Pb/PbO2), NaS, Ni/Cd, NiMH(metal hydride), Ni/Zn, Zn/AgO, Zn/MnO2, Zn/Br2; and primary(non-rechargeable) batteries: Zn/MnO2, AgCl/Mg, Zn/HgO, Al/Air (~2) ~ Zn/Air(O2), Li/SO2, Li/Ag2CrO4 and Li/MnO2 exist.
Although a variety o~ batteries are available, the lead-acid battery remains favored ~or uses such as starting internal combustion engines, electric vehicle motive power, as well as portable and emergency power ~or industrial and military applications.
Lead-acid batteries include a cathode comprising a lead alloy grid (active material support structure and electrical network structure contact with the battery t~rmin~ls) having PbO2 active material thereon; and an anode comprising sponge lead on a grid. The active material on a grid is called the plate and electrically, the anode (Pb) plate is negative and the cathode (PbO2) plate is positive. A separator, either glass fibers or porous plastic, is used to separate the cathode and anode from direct contact when the plates are in sulfuric acid electrolyte. For the lead-acid battery, the rated capacity W O 97/12410 PCT~US96/15621 (ampere-hours) depends on the total amount of electrochemically active material in the battery plates, the concentration and amount of sulfuric acid electrolyte, the discharge rate and the percent utilization (conversion of active material into ampere-hours)for the active materials (the cathode or PbO2 usually being the limiting factor).
During discharge of a lead-acid battery, the lead and lead dioxide active materials are converted to lead sul~ate.
The lead sulfate can form an undesirable, insulating layer or passivation around the cathode active material particles which reduces the active material utilization during discharge. This passivating layer can be the result of improper battery charging, low temperature operation, and/or excessive (high current) discharge rates. In order to increase the cathode active material utilization, which is desirable for battery performance, means to increase the cathode active material porosity which increases the amount of active material contact with the sulfuric acid and/or active material conductivity which minimizes resistance and electrical isolation of the active material particles are useful. However, raising the cathode active material porosity tends to increase the tendency ~or a loosening and possible loss of active material from the plate as well as electrical isolation o~ the active material from the grid structure. Wrapping the cathode plate with a glass mat holds the loosened active material tightly to the plate and mini~i zes the tendency ~or active material sediment (electrochemically lost cathode material) in the bottom o~ the battery container. The addition of conductive materials (carbon, petroleum coke, graphite) to increase the conductivity of the cathode active material is well-known, but these materials are degraded rapidly ~rom the oxygen generated at the cathode during charging.
Since the lead-acid battery anode is very conductive, the additives for the sponge lead active material have concentrated on improving low temperature battery per~ormance W O 97/12410 PCT~US96/15621 and cycle li~e. The ~undamental additive to the anode is the expander which is comprised o~ lampblack, barium sul~ate and lignosul~onic acid mixed with the lead oxide (PbO) carrier agent. The expander addition to the sponge lead inhibits densi~ication or decrease in the sponge lead porosity. If the anode active material becomes too dense, it is unable to operate at low temperatures and can no longer sustain practical current discharges.
In the manu~acture o~ lead-acid batteries, cathode electrodes are usually prepared ~rom lead alloy grids which are ~illed with an active paste that contains sul~ated lead oxide. This sulfated lead oxide is then later converted or ~ormed into sponge lead ~or the anode and lead dioxide ~or the cathode. In an alternative construction, known as tubular cathode plates, the cathode active material is a sul~ated lead oxide powder that is poured into a non-conductive tube (braided or woven glass or polyethylene) containing a protruding lead alloy rod or spine. Several o~ these tubes make up the grid structure and electrical connections are made to the ter~i n~ ls by the protruding lead alloy rods. The tubular cathodes and the usual plate anodes are then assembled into elements and these are then placed in a battery container. The cells are ~illed with electrolyte and the battery is subjected to the ~ormation process. See details on lead-acid batteries, by Doe in Kirk-Othmer: Encyclopedia o~
Chemical Technology, Volume 3 (1978), page 640-663.
During lead-acid battery ~ormation, active material particles in contact with the grid are ~ormed ~irst and particles ~urther away ~rom the grid are ~ormed later. This tends to reduce the e~iciency o~ ~ormation. An apparent solution to this problem is addition o~ a conductive material to the active material paste. The additive should be electrochemically stable in the lead-acid system both with respect to oxidation and reduction at the potentials experienced during charge and discharge o~ the cell, as well W O 97/12410 PCT~US96/15621 as to chemical attack by the sulfuric acid solution. The use o~ barium metaplumbate and other ceramic perovskite powder and plating additives to the lead-acid battery anode and cathode are reported to enhance the ~ormation o~ lead-acid batteries.
See U. S. Patent No. 5,045,170 by Bullock and Kao. However, these additives are limited to the lead-acid battery system and require up to a 50 weight percent addition to be e~ective.
For other battery systems, the cathode materials such as, MoO3, V205 Ag2CrO4 and (cFx) n that are used in primary lithium batteries are typically mixed with carbon, metal or graphite powder to improve the overall cathode electrical conductivity and therefore, the utilization of the cathode material.
Depending on the battery design, the current collector is either the cathode material itsel~ or a nickel screen pressed into the cathode material- The current collector ~or the anode (lithium) is a nickel screen pressed into the lithium metal.
The separator between the lithium battery cathode and anode is typically a non-woven polypropylene, Te~lon or polyvinyl chloride membrane. The elect~olyte ~or the lithium battery is an organic solvent such as propylene carbonate,dimethyl sulphoxide, dimethyl~ormamide, tetrahydro~uran to which some inorganic salt such as, LIC104, LiCl, LiBr, LiAsF6 has been added to improve the solution ionic conductivity. Hughes, Hampson and Karunathilaka (J-=~ower Sources, 12 (1984), pages 83-144)) discuss the enhancement techniques used ~or improving the cathode electrical conductivity ~or lithium anode cells.
While the addition o~ the materials to improve the cathode conductivity and utilization are ~easible, the amount o~
additive material required means that much less electrochemical active cathode material that will be available, and in some lithium battery designs, because o~
volume limitations, that can be critical Other battery systems requiring that the cathode have improved conductivity and thereby, improved cathode W O 97/12410 PCTAUS96/1~621 (NiOOH/Ni(OH)2) active material utilization are secondary nickel batteries such as, Ni/Cd, Ni/Zn and Ni/MH (metal hydride). The electrolyte ~or the nickel battery system is usually potassium hydroxide solution and the separator between the anode and cathode is non-woven polypropylene. To enhance the cathode conductivity, graphite is added but this material is not long lasting as it is gradually oxidized to carbon dioxide. In addition to the degradation o~ the graphite/ there is a gradual build-up o~ carbonate ions which reduces the conductivity o~ the electrolyte. See discussion on nickel batteries in "Maintenance-Free Batteries" by Berndt.
A sodium-sul~ur battery comprises molten sul~ur or molten sodium polysul~ide as a cathode, molten sodium as an anode, and a non-porous solid electrolyte made o~ beta alumina that permits only sodium ions to pass. The sul~ur or sodium polysul~ide in the cathode has an in~erior electrical conductivity in itsel~. The art has attempted to address this problem by adding conductive ~ibers such as metal ~iber or carbon ~iber to the molten sul~ur or molten sodium polysul~ide. For general in~ormation, see U.S. Patent Numbers 3, 932,195 and 4,649,022. These types o~ ~ibers however, are prone to corrosion in the electrochemical environment o~ a sodium-sul~ur battery. A need there~ore continues ~or sodium-sul~ur batteries which employ chemically stable conductive ceramic materials therein.
Another type o~ electrical energy generating device, as is known in the art, is the ~uel cell such as acid ~uel cells, molten carbonate ~uel cells, solid polymer electrolyte ~uel cells and solid oxide ~uel cells. A ~uel cell is an apparatus ~or continually producing electric current by electrochemical reaction o~ a ~uel with an oxidizing agent.
More speci~ically, a ~uel cell is a galvanic energy conversion device that chemically converts a ~uel such as hydrogen or a hydrocarbon and an oxidant that catalytically react at electrodes to produce a DC electrical output. In one type o~

fuel cell, the cathode material defines passageways for the oxidant and the anode material defines passageways for ~uel.
An electrolyte separates the cathode material from the anode material. The ~uel and oxidant, typically as gases, are continuously passed through the cell passageways ~or reaction.
The essential difference between a fuel cell and a battery is that there is a continuous supply of ~uel and oxidant from outside the fuel cell. Fuel cells produce voltage outputs that are less than ideal and decrease with increasing load (current density). Such decreased output is in part due to the ohmic losses within the ~uel cell, including electronic impedances through the electrodes, contacts and current collectors. A
need therefore exists for fuel cells which have reduced ohmic losses. The graphite current collectors used in phosphoric acid and solid polymer electrolyte fuel cells, to the cathode metal oxides such as, praseodymium oxide, indium oxide used in solid oxide fuel cells and to the nickel oxide cathode used in molten carbonate fuel cells are examples o~ a need for conductive additives. See generally, "Handbook of Batteries and Fuel Cells", Edited by Linden.
Multilayer surface mount ceramic chip capacitors which store electrical energy are used extensively by the electronics industry on circuit boards. A typical multilayer surface mount chip capacitor is comprised of alternating multilayers of dielectric (ceramics such as BaTiO3) electrodes (metals such as Pd or Pd-Ag). The end caps or termin~tions of the capacitor are typically a metallic (Ag/Pd) in combination with a conductive glass. This termination is the means o~
contact to the internal electrodes of the multilayer ceramic capacitor. The development of other electrodes such as nickel and copper to reduce costs and the use o~ low cost conductive additives to the glass are actively being sought. See generally, Sheppard (American Ceramic Society Bulletin, Vol.
72, pages 45-57, 1993) and Selcuker and Johnson (American Ceramic Society Bulletin, 72, pages 88-93, 1993).

W O 97/12410 PCTnUS96/~5621 An ultra-capacitor, sometimes re~erred to as a super capacitor, is a hybrid encompassing per~ormance elements o~
both capacitors and batteries. Various types o~ ultra-capacitors are shown in "Ultracapacitors, Friendly Competitors and Helpmates ~or Batteries, n A.F. Burke, Idaho National Engineer Laboratory, February 1994. A problem associated with an ultracapacitor is high cost o~ manu~acture.
Sensors, as are known in the art, generate an electrical potential in response to a stimulus. For example, gas sensors such as oxygen sensors generate an electrical potential due to interaction o~ oxygen with material o~ the sensor. An example o~ an oxygen sensor is that described by Takami (Ceramic Bulletin,6~, pages 1956-1960, 1988). In this design, the sensor material, titania (TiO2), is coated on an alumina (Al2O3) substrate with individual lead connections ~or the substrate and the titania components. The development o~
higher electrical conductive titania to improve the oxygen sensor response is an on-going process. Another sensor, humidity, is based upon the electrical conductivity o~ MgCr2O4-TiO2 porous ceramics is discussed by Nitta et al. (J. American Ceramic Society, 63, pages 295-300, 1980). For humidity sensing, leads are placed on both sides o~ the porous ceramic plaque and the sensor is then placed in the air-moisture stream ~or resistivity (inverse o~ electrical conductivity) measurements. The relative humidity value is then related to the measured resistivity value. With this design, the porous ceramic resistivity value, as low as possible, is critical because o~ the need ~or a rapid measurement response time (seconds) that can be related to an accurate relative humidity value.
Another type o~ electrical device, as is known in the art, is a bipolar battery. Such a battery typically comprises an electrode pair constructed such that cathode and anode active materials are disposed on opposite sides o~ an electrically conductive plate, that is, a bipolar plate. The W O 97/12410 PCT~US96/15621 cells that have this electrode pair are configured such that the cell-to-cell discharge path is comparatively shorter and dispersed over a large cross-sectional area, thus providing lower ohmic resistance and improved power capabilities compared to unipolar batteries such as automobile batteries.
The bipolar electrodes are stacked into a multicell battery such that the electrolyte and separators lie between adjacent bipolar plates. The Lead-acid batteries are attractive candidates for bipolar construction because of the high power capabilities, known chemistry, excellent th~rm~l characteristics, safe operation and widespread use. However, such lead-acid batteries with bipolar construction often fail due to the corrosion of the electrically conductive plate when in contact with the active material. A need there~ore exists for bipolar batteries which have improved corrosion resistance, low resistivity and reduced weight. For general information on bipolar batteries, see Bullock (J.
Electrochemical Society, 142, pages 1726-1731, 1995 and U. S.
Patent No. 5,045,170) and U. S. Patent No. 4,353,969.
Although the devices o~ the prior art are capable o~
generating and storing electrical energy, and acting as oxygen and relative humidity sensors, there is a need ~or improved materials o~ construction for reasons o~ ~iminished corrosion, higher capacity and/or higher electrical conductivity which overcome the disadvantages of the prior art.
In addition to the previously mentioned materials used in the above applications, there are several U S. Patents which delineate the electrochemical use o~ electrically conductive ceramics such as the sub-oxides o~ titanium which are formed ~ro~ the reduction o~ titanium dioxide in hydrogen or carbon monoxide reducing gases at high temperatures (1000~C or greater). For example, U. S. Patent No. 5,126,218 discusses the use of TiOX (where x=1.55 to 1.95) as a support structure (grids, walls, conductive-pin separators), as a conductive paint on battery electrodes and as powder in a plate ~or the CA 02233337 l998-03-27 W O 97/12410 PCTrUS96/15621 lead-acid battery A similar discussion occurs in U. S. Patent No 4,422,917 which teaches that an electrochemical cell electrode is best made ~rom bulk material where the TiO~ has its x vary ~rom 1.67 to 1.85, 1.7 to 1.8, 1.67 to 1.8, and 1.67 to 1.9.
The said mentioned electrode materials are suitable ~or electrocatalytically active sur~aces when it includes material ~rom the platinum group metals, platinum group metal alloys, platinum group metal oxides, lead and lead dioxide. The electrodes are also suitable ~or metal plating, electrowinning, cathodlc protection, bipolar electrodes ~or chlorine cells, tile co~struction, and electrochemical synthesis o~ inorganic and organic compounds.
Oxides o~ titanium are discussed in U. S. Patent No.
5,173,215 which teaches that the ideal shapes ~or the Magneli phases (TinO2~_1where n is 4 or greater) are particles that have a diameter o~ about one micron (1 micron (denoted u) is 10-6 meter (denoted m)) or more and a sur~ace area o~ 0.2 m2/g or less.
The U. S. Patent No. 5,281,496 delineates the use o~ the Magneli phase compounds) in powder ~orm ~or use in electrochemical cells. The use o~ powder is intended for the electrode structure only.
U. S. Patent No. 4,931,213 discusses a powder containing the conductive Magneli phase sub-oxides o~ titanium and a metal such as copper, nickel, platinum, chromium, tantalum, zinc, magnesium, ruthenium, iridium, niobium or vanadium or a mixture o~ two o~ more o~ these metals.

DIS~LOSURE OF THE INVFN~IQ~
The invention is directed to solving the problems o~ the prior art by improving electrochemical devices such as batteries, ~uel cells, capacitors, sensors and other electrochemical devices as ~ollows: (1) In batteries ~or example, there will be an improved discharge rate, increased CA 02233337 l998-03-27 W O 97/12410 PCTrUS96/15621 electrochemically active material utilization, improved charging efficiency, reduced electrical energy during the formation of electrochemically active materials and decreased electrical resistance of the electrochemically active material matrix; (2) In fuel cells, for example, there will be decreased electrical resistance of the current collectors and cathode materials as well as increased electrical chemical efficiency o~ the reactants; (3) In capacitors, for example, there will be development of less expensive electrodes and conductive glass; (4) In sensors, there will be the development of lower resistive titanium dioxide for oxygen sensors and lower resistive binary compounds containing titanium dioxide for relative humidity sensors; and (5) In other electrochemical devices, for example, there will be the development of more corrosion resistant and current e~icient electrodes ~or electrolysis, electrosynthesis.
As used herein, conductive ceramic materials include conductive ceramic compositions such as solids, plaques, sheets (solid and porous), fibers, powders, chips and substrates (grids, electrodes, current collectors, separators, ~oam, honeycomb, complex shapes for use in components such as grids made by known methods such as weaving, knitting, braiding, felting, ~orming into paper-like materials, extrusion, tape casting or slip casting) made from conductive ceramic compositions having metal containing additives and metallic coatings thereon, or made ~rom non-conductive ceramic compositions having metal containing additives and metallic coatings dispersed thereon.
The electrically conductive ceramic materials for use in the invention, when in the ~orm of fibers, powders, chips or substrate, are inert, light weight, have high sur~ace area per unit weight, have suitable electrical conductivity, as well as high corrosion resistance. Typically, the electrically conductive ceramic fibers, powders, chips or substrate herein have an electrical conductivity of 0.1 (ohm-cm)-l or more.

CA 02233337 l998-03-27 Electrically conductive ceramic ~ibers, powder, chips or substrate useful in the invention include an electrically conductive or non-electrically conductive ceramic matrix, preferably with a metal cont~i n i ng additive and/or metallic coating. Ceramic matrix materials which may be employed include, the oxides o~ the metals titanium, and vanadium and the oxides o~ zirconium, and aluminum. The reduced oxides o~
titanium and vanadium have a certain amount o~ intrinsic electrical conductivity and the oxides o~ zirconium and aluminum are intrinsically insulators All mentioned ceramic oxides have di~erent chemical and physical attributes and these materials cover a wide range o~ applicability. Either ceramic metal oxide can have the electrical conductivity increased by the addition or plating or coating or deposition o~ singly or a mixture thereo~ o~ metallic d-block transition elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, H~, Ta, W, Re, Os, Ir, Pt, Au), Lanthanides (Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu) and/or by the addition or plating or coating or deposition singly or a mixture thereo~ of selected main-group elements (B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te) and/or the oxides, halides, carbides, nitrides and borides o~ the a~orementioned elements. Chemical reduction processes ~or the selected mixtures reduce the ceramic to its ~inal electrically conductivity form. Similarly, chemical oxidation processes may be used to ~orm superstoichiometric titanium oxide in which the atomic oxygen to titanium ratio is slightly above 2.
The electrically conductive ceramic materials, ~ibers, powders, and chips mentioned in this invention can be used to enhance the electrical conductivity and thereby, the utilization o~ the electrochemically active materials in cathode for the ~ollowing primary and secondary battery systems: lithium batteries, zinc air batteries, aluminum air batteries, alkaline batteries, Leclanche batteries, nickel W O 97/12410 PCTrUS96/15621 batteries, lead-acid batteries, and sodium-sulfur. The electrically conductive ceramic substrate as mentioned in this invention would be suitable for fuel cell electrodes and current collectors and bipolar plate batteries. In addition, the electrically conductive ceramic materials, fibers, powders, chips and substrate according to this invention would be suitable for oxygen and humidity sensors as well as multilayer chip capacitors and ultracapacitors. The electrode made from this invention can also be useful as an anode or cathode, whichever is applicable, in electrochemical devices including batteries and in an electrolytic cell generating ozone, chlorine gas, or sodium, recovering metals from wastewater and purification of metals by electrolysis.
The electrically conductive ceramic materials, fibers, powders, chips and/or substrates therein may impart superior battery discharge and charging performance, battery cycle life, battery charge retention, battery weight reduction, deep battery discharge recovery, as well as battery structure vibration and shock resistance Batteries such as lead-acid batteries which employ electrically conductive ceramic materials, fiber, powder, chips and/or substrates therein advantageously may require reduced electrical energy during formation. Fuel cells utilizing electrically conductive ceramic materials, fibers, powder and/or substrate for the current collector and the electrodes may have longer operating life because of superior corrosion resistance and enhanced performance because of superior electrical conductivity. The use o~ electrically conductive ceramic materials, fibers, powder, chips and substrates from this invention may impart low cost manu~acturing, superior electrical resistivity performance in oxygen and humidity sensors, multilayer chip capacitors, and ultracapacitors.
Other advantages of the present invention will become apparent as a fuller understanding o~ the invention is gained ~rom the detailed description to follow.

W O 97/12410 PCT~US96/1~621 MODF.S FOR CARRYING OUT THE INVENTION
In accordance with the invention, electrically conductive ceramic materials, ~ibers, powders, chips and substrates are either added to components or used to construct components ~or electrochemical devices such as batteries, fuel cells, capacitors, sensors, and other electrochemlcal devices. The type o~ conductive ceramic material used depends on the type o~ chemical, electropotential and electrochemical environments to which the conductive ceramic materials will be subjected.
Pre~erred Ceramic Materials The pre~erred starting materials ~or electrically conductive sub-oxide titanium ceramics according to this invention are the ~ollowing: TiO2 (pre~erably rutile), Ti, Ti203 Ti305, metal (chromium, copper, nickel, platinum, tantalum, zinc, magnesium, ruthenium, iridium, niobium, and vanadium or a mixture o~ two or more of the a~orementioned metals)-containing intercalated graphite, graphite and carbon.
Also possible, the addition o~ singly or a mixture thereo~
metallic d-block transition elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, H~, Ta, W, Re, Os, Ir, Pt, Au), Lanthanides (Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu) and by the addition singly or a mixture thereo~ selected main-group elements (B, Al, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te) and/or the oxides, halides, carbides, nitrides and borides o~ the a~orementioned elements. All materials used should have a purity level that excludes deleterious substances ~or this process as well as the projected use.
The preferred starting materials ~or electrically conductive sub-oxide vanadium ceramics according to this invention are the :Eollowing: V205, V2O3, VO2, V, metal (chromium, copper, nickel, platinum, tantalum, zinc, magnesium, ruthenium, iridium, niobium, and vanadium or a W O 97/12410 PCT~US96/15621 mixture of two or more of the aforementioned metals)-containing intercalated graphite, graphite, and carbon. Also possible, the addition of singly or a mixture thereof metallic d-block transition elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au), Lanthanides (Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu) and by the addition singly or a mixture thereof selected main-group elements (B, Al, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te) and/or the oxides, halides, carbides, nitrides and borides of the aforementioned elements. All materials used should have a purity level that excludes deleterious substances for this process as well as the projected use.
The teachings of U. S. Patent No. 4,422,917 state that - the conductive materials of choice for the sub-oxides of titanium should consistent essentially of Ti407and Ti509 in order to maximize the conductivity. This concept was further extended by the teachings of U. S. Patent No. 5,173,215 which stated that it is more proper to speak of the appropriate conductive sub-oxides of titanium as Magneli phases with the general formula TinO2n1where n=4 or greater. TiO is never considered in either patent as an important component because of reported instability and less than desirable resistance to chemical attack. For the sub-oxides of titanium, Ti407has been measured with a conductivity value of 1585 (ohm-cm)~1, Ti509 has been measured with an electrical conductivity value of 553 (ohm-cm)~1, and the electrical conductivity of TiO has been measured to be 3060 (ohm-cm)~1. This TiO value is almost twice that of the Magneli phase Ti407. With this invention, the TiO
is considered to be an important component o~ the over-all electrical conductivity. Through judicious selection of the sub-oxide titanium reduction process conditions to make a well-defined TiO structure and with the aforementioned metal compound additions to the starting materials for the titanium oxides, a synergism e~fect occurs during processing and W O 97/12410 PCTnUS96/15621 results in a stable and chemical resistance TiO structure within the ceramic matrix of the sub-oxides of titanium.
Separately, the ~917 and l215 patents do not teach super-oxides of titanium tsuperstoichiometric "TiO2") in which the atomic oxygen to titanium ratio is slightly above 2.
A pre~erred composition of matter for the electrically conductive ceramic material, fibers, powders, chips and substrates of the sub-oxides of titanium with additives is as follows:
ConstituentWeight Percent(%) TinO2n_l where n=4 or greater80-90 TiO 0-10 Ti2O3and Ti305 ~>>1 M oxides, and/or borides, and/or carbides, 0-10 and/or nitrides and/or ~ree metal, wherein the sum of the above percentages is less than or equal to 100% and wherein M=
Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, H~, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, B, Al, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te.
Another composition of matter for the electrically conductive ceramic material, fibers, powders, chips and substrates of the sub-oxides of titanium, if there were no metal compound additives, and i~ the starting materials were only TiO2 (preferably rutile) and metal-containing intercalated graphite, is:
ConstituentWeight Percent(%) TinO2n_1where n=4 or greater90-100 M oxides and/or free metal Where M= Cr, Cu, Ni, Pt, Ta, Zn, Mg, Ru, Ir, Nb, V. 0-10 A preferred composition o~ ~atter ~or the electrically conductive ceramic material, ~ibers, powders, chips and CA 02233337 l998-03-27 substrates o~ the sub-oxides of vanadium with additives is as follows:
Constituent Weight Percent(%) VOx (x=1 to 2.5) 50-90 M oxides, and/or borides, and/or carbides, and/or nitrides and/or free metal 10-50 wherein the sum of the above-noted weight percents is less than or equal to 100 and wherein M= Sc, Ti, V, Cr, Mn, Fe, Co, .
Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, b, Al, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te.

Another composition of matter for the electrically conductive ceramic material, fibers, powders, chips, and substrates o~ the sub-oxides of vanadium, if there were no metal compound additives, and if the starting materials were only V2O3 and metal-containing intercalated graphite, is:
Constituent Weight Percent(%) VOx (x = 1 to 2.5) 90-100 M oxides and/or free metal Where M= Cr, Cu, Ni, Pt, Ta, Zn, Mg, Ru, Ir, Nb, V either singly or mixtures thereof 0-10 For electrically conductive ceramics made by plating, coatings, and deposition of metals and/or conductive ceramic, the composition of matters are as follows:
Constituent Weight Percent(%) Al203 85-90 M oxides and/or free metal 5-15 Where M= Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, In, Tl, Sn, Pb, Sb, Bi, Se, Te either singly or mixtures thereof.

CA 02233337 l998-03-27 ConstituentWeight Percent(%) Zr~2 85-95 M oxides and/or ~ree metal 5-15 Where M= Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, 1u, B, Al, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te singly or mixtures thereo~.

Constituent Weight Percent(%) ZrO2 40-48 M oxides and/or ~ree metal 4-20 Where M= Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, H~, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, B, Al, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te, singly or mixtures thereo~.
Examples o~ applications in which the conductive ceramic materials o~ the present invention can be used are the ~ollowing: (1) the use o~ ~ibers, powder, or chips in the cathode active materials of the lead-acid, lithium, nickel, Zn, and metal air batteriesi (2) the use o~ ~ibers, powder or chips to make substrates ~or use as current collectors and electrodes and the use o~ ~iber, powder, and chips in electrodes ~or ~uel cellsi (3) the use o~ ~ibers, powders or chips to make substrates ~or use as electrodes ~or electrosynthesis, cathodlc protection, electrocatalysis, electrolysis, and metal recovery; (4) the use o~ ~ibers, powder and chips to make substrates which can act as bipolar electrode construction ~or lead-acid batteries; (5) the use ~ibers, powders and chips to make substrates ~or use as electrodes and the use o~ ~ibers and powder in glass ~or capacitors; (6) the use o~ ~ibers, powders, chips to make a substrate which can act as an electrode in sensors. I~ so desired, the electrodes ~abricated ~rom this invention can be W O 97/12410 PCT~US9~/15621 plated, coated, or deposited with metals to enhance their electrochemical properties.

Forming o~ Shaped Materials Electrically conductive ceramic materials and ~ibers can be ~ormed ~rom the oxides of titanium or vanadium material that may or may not have metal containing additives and "in situ" reduction agents dispersed therein. Shaping may be done on either electrically-conducting or electrically non-conducting materials. In the latter case, activation o~ the oxide to a conducting state is done on the shaped material.
For titanium or vanadium materials, this activation may be done by chemical reduction. Normally non-conducting oxides such as Al2O3 or ZrO2 are made conducting by plating of conducting materials, as is discussed below. In the ~ollowing, various possible shapes are discussed.

Fibers These ceramic matrixes are made into ~ibers by known fiber-making processes such as the viscous suspension spinning process (Cass, Ceramic Bulletin, Vol 70, pages 424-429, 1991) with and without metal-containing intercalated graphite, or by the sol-gel process (Klein, Sol-Gel Technology for Thin Films, Fibers, Pre~orms, Electronics, and Speciality Shapes, Noyes Publications, pages 154-161), and or by either the slurry or solution extrusion process ~Schwartz,Handbook of Structural Ceramics, page 4.55, 1992). The procedures ~or sample slurry or slip preparation, drawing or extruding material as well as the appropriate drying to remove water, heating to burn o~
organics, and sintering are discussed in detail in these articles. A~ter the sintering operation at 1000-2000~C, these ceramic ~iber materials are made electrically conductive through reduction in a ~urnace at 1000-2000~C whose atmosphere is either hydrogen, carbon monoxide or mixtures o~ these gases. In addition, depending on the metal containing CA 02233337 l998-03-27 W O 97/12410 PCT~US96/15621 additives in the starting ceramic matrix, "in situ" reduction and/or decomposition processes occur during the drying, heating, sintering and reduction cycles via the use o~ "in situ" reduction materials such as carbon, metal-cont~i n ing intercalated graphite, graphiter and metal powders incorporated either singly or mixtures thereo~ into the ceramic matrix. Once a~ter the reduction process has ended, the ~ibers are cooled ln a dry atmosphere and stored until use. ~t this point, the electrically conductive ceramic ~ibers are now ready ~or use. All initial starting materials are in powdery ~orm and the ceramic matrlx powders have been mixed to obtain a homogeneous mixture o~ ~aterials be~ore preparing the slurry or slip prior to the ~iber making process. For enhanced ceramic matrix reactivity, it is pre~erred that the particle size o~ the powders be in the range o~ 40 to 150 microns.
Pre~erably, the electrically conductive ceramic ~ibers have an aspect ratio o~ greater than 1 and an electrical conductivity value o~ 0.1 (ohm-cm)~1or greater.
Non-electrically conductive ceramic ~ibers are ~or~ed ~rom alumina (Al2O3) or zirconia (ZrOz) or zirconia-alumina material with no metal containing additives or "in situ"
reduction agents. These ceramic matrixes are then made into ~ibers by the previously mentioned viscous suspension spinning process, or by the sol-gel process, and/or by either the slurry or solution process. The sample slurry or slip preparation, drawing or extruding material as well as the appropriate drying to remove water, heating to burn o~
organics, sintering and storage conditions are the same as discussed ~or the electrically conductive ceramics matrixes.
All the initial starting materials are in powdered ~orm and are mixed to obtain a homogeneous mixture be~ore slurry or slip preparation prior to the ~iber-making process. It is pre~erred that the particle size o~ the starting powders be in the range o~ 40 to 150 microns. The ceramic ~ibers so obtained CA 02233337 l998-03-27 WO 97/12410 PCT~US96/15621 are considered to be insulators or non-electrically conductive.

Details o~ Spinning and Sintering to Make Fibers In ~orming the conductive ceramic ~ibers by solution spinning and sintering, a suspension o~ particles of ceramic material in a solution o~ destructible carrier dissolved in a solvent is prepared. The ~ibers then are wet or dry spun ~rom the suspension, dryed and fired to drive o~ the carrier and sinter the ~iber. Pre~erably, the particle size is 5 microns or less, and polyvinyl alcohol/ water system may be used as a carrier/solvent.
After the a~orementioned components have been mixed at a certain compositional ratio characteristic o~ the desired ceramic material, the resulting mixture is dispersed or dissolved in a polymer compound solution. Thus, a spinning solution is obtained. Optionally, the a~orementioned mixture may be roasted at an elevated temperature such as 900-1,100~C
~or about 1-5 hours before it is dispersed or dissolved in the polymer compound-containing solution.
Examples o~ polymer compounds which may be used in the present invention include polyacrylonitrile, polyethylene, polypropylene, polyamide, polyester, polyvinyl alcohol polymers ("PVA"), cellulose derivatives (e.g., methyl cellulose, hydroxyethyl cellulose, hydroxyethylmethyl cellulose, etc.), polyvinylpyrrolidone, polyacrylamide, polyethylene glycol, etc.
Generally, the degree o~ saponi~ication o~ the a~orementioned PV~ polymer may be 70-100 mol%, more pre~erably 85-100 mol~, most pre~erably 95-100 mol~-O. The degree o~
polymerization o~ the polymer may be 500-20,000, pre~erably 1,000-15,000.
Polyvinyl alcohol polymers which may be employed include ordinary unmodi~ied polyvinyl alcohol as well as modi~ied polyvinyl alcohols can also be used. ~s modi~ied polyvinyl W O 97/12410 PCTrUS96/15621 alcohols, a saponi~ied copolymer o~ vinyl acetate and a copolymerizable comonomer may be used. Examples o~ these comonomers include vinyl esters such as vinyl propionate, vinyl stearate, vinyl benzoate, vinyl saturated branched ~atty acid salts, etc., unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crontonic acid, etc. and their alkyl esters, unsaturated polycarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. and their partial esters or total esters, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, ole~insul~onic acids such as ethylenesul~onic acid, allylsul~onic acid, methacrylsul~onic acid, etc. and their salts, ~-ole~ins such as ethylene, propylene, butene, ~-octene, ~-dodecene, ~-octadecene, etc., vinyl ether, silane-containing monomers, etc. The concentrations o~ the a~orementioned comonomers with respect to the copolymer may be less than 20 mol%.
As other modi~ied polyvinyl alcohols, products obtained by modi~ying a vinyl acetate homopolymer or the a~orementioned saponi~ied copolymer can be used. Examples o~ modi~ying reactions include acetylation, urethanation, phosphoric acid esteri~ication, sul~uric acid esterl~ication, sul~onic acid esteri~ication, etc.
A use~ul spinning solution ~or ~orming fibers ~or use in the present invention may be obtained by dispersing or dissolving a ceramic material or a substance which can be converted to a conductive ceramic material by heat treatment (pre~erably a ~iber) in the a~orementioned polymer compound solution.
As the solvents o~ the polymer compound solution, water or other solvents which can solubilize polymer compounds may be used.
Examples o~ solvents other than water include alcohols, ketones, ethers, aromatic compounds, amides, amines, sul~ones, etc. These solvents may be mixed with water at certain ratios.

WO97/12410 PCT~US96/15621 Polyvinyl alcohol polymers may be employed as the polymer compound. The solvents such as water, dimethyl sul~oxide, glycerin, ethylene glycol, diethylene glycol, N-methylpyrrolidone, dimethylformamide, and their mixtures can be advantageously used.
In the present invention, dry spinning may be employed to produce ~ibers ~or use in the claimed invention. As is known in the art, dry spinning entails spinning a solution drawn into air or another gas ~rom a die or in a die-~ree state.
The spinning dra~t typically is about 0.1-2Ø Subsequently, the resulting precursor ~iber is heat-treated. The precursor ~iber may be stretched be~ore heat treatment. In a typical heat treatment, the ~iber is baked ~or several minutes to several hours in a desired atmosphere to achieve a desired level of conductivity in the ~iber. Then, the ~iber is cooled.
There are no special restrictions on the diameter o~ the conductive ~iber obtained. Typically, the diameter is about 200 um or less, preferably 100 ~m or less, more pre~erably 50 ~m or less, most pre~erably 20 ~m or less. There are no special restrictions on the lower limit.
In the a~orementioned spinning solution, the weight ratio o~ the polymer compound with respect to the conductive ceramic material or substance which can be converted to conductive ceramic material by heat treatment is about 15 wt~ or less and 3 wt% or more, pre~erably 10 wt% or less and 3 wt% or more, respectively.
When the a~orementioned spinning solution is prepared, a dispersant ~or the conductive ceramic material or substance which can be converted to conductive ceramic material by heat treatment can also be used. Examples o~ dispersants include anionic emulsi~iers, nonionic emulsi~iers, and cationic emulsi~iers such as polyoxyethylene (10) octylphenyl ether and sodium dodecylsul~ate. Moreover, polyacrylic acid and its salts, polystyrene, neutralized maleic anhydride copolymers, W O 97/12410 PCTnUS96/15621 maleic anhydride-isobutene copolymer, and other polymer dispersion stabilizers may be used.
There are no special restrictions on the total solid content o~ the aforementioned spinning solution. Generally speaking, however, the solid content is about 20-70 wt%.
A~ter the spinning solution has been dry-spun, it is dried.
Thus, a continuous precursor ~iber is obtained.
Sintering o~ mixtures o~ ceramic powders, optionally with metals, may also be employed to manu~acture conductive ceramic ~ibers. In the manu~acture o~ conductive ceramic materials by sintering, ceramic matrix material and metal additive are combined with a binder, and subjected to elevated temperatures in a selected atmosphere. The speci~ic temperatures and the atmosphere depend on the composition to be sintered. See ~or example, U.S.Patent 4,931,213 directed to sintering o~
substoichiometric TiO2 having Cu therein. Metal containing additives which may be incorporated into the ceramic matrix by sintering have a relatively high melting point and a low vapor pressure to m; nim; ze loss o~ the metal containing additive.
Metals which may be included in ceramic matrices to provide conductive ceramic material ~or use in the invention include Cu, Ni, Co, Ag, Pt, Ta, Zn, Mg, Ru, Ir, Nb, V, Sn, SnO, SnO2, Pb, and alloys thereo~, as well as other metals which are stable in the electrochemical system of the device. For example, conductive ceramic ~ibers ~ormed o~ non-stoichiometric TiO2 such as Ti407 and/or Ti509 matrix having Cu therein may be employed.

Coating o~ ~ibers The conductive ceramic ~ibers employed in the invention may be coated with a metal such as Cu, Ni, Co, Ag, Pt, Ta, Zn, Mg, Ru, Ir, Nb, V, W, Sn, SnO, SnO2, Pb, as well as alloys thereo~. Choice o~ metal coating on the conductive ceramic materials and ~ibers depends on the active material, and/or the component in which the coated conductive ceramic ~ibers 2~

CA 02233337 l998-03-27 W O 97/12410 PCT~US96/15621 are employed. For example, in lead-acid batteries, especially useful metal coatings include Sn-Pb alloys wherein Sn may be up to 90%, remainder Pb in thicknesses o~ about 0.1-1.0 mil on a conductive ceramic ~iber material o~ either Ti407 and/or Tis~s In alkaline batteries such as NiCd, NiMH, Ni-Fe, Ni-Zn and MnO2-Zn, especially use~ul metal coatings include Ni, Ag and Cu in thicknesses o~ about 0.1-1.0 mil on a conductive ceramic ~iber matrix o~ substoichiometric TiO2 such as Ti407 and/or TisO5 intercalated with Cu.
In Li batteries such as Li-MnO2, especially use~ul coatings include Ni, Ag, Cu, Li, and SnO2 in thicknesses of about 0.1-1.0 mil on a conductive ceramic ~iber matrix o~
substoichiometric TiO~ such as Ti407 and/or Tis~s~
In Ni batteries such as NiCd, and NiMH, especially use~ul metal coatings include Co, Ni, NiCo alloys on a ceramic matrix o~ Ti407 and/or Ti509, each o~ which optionally may have Cu therein. In sensors such as gas sensors, especially use~ul coatings include SnO2 on, ~or example, TigO7 and/or TisOg ceramic matrix, each o~ which may have Cu therein.
In capacitors such as TiO2 on TigO7 and/or Ti509, carbon or graphite on Ti407 and/or Ti509, especially use~ul coatings include Cu on a ceramic matrix o~ TigO7 and/or TisOg.
The speci~ic choice o~ conductive ceramic matrix material and metal containing additive therein, as well as the composition o~ metal coating thereon, may be determined by the art skilled in accordance with the speci~ic electrochemical system o~ the device in which the ~ibers or other conductive ceramic materials are employed. The primary requirements are that the ~iber or other conductive ceramic materials and metal coating be compatible with the electrochemistry o~ the battery. Accordingly, the choice o~
metal coating on the conductive ceramic ~iber or material will vary depending on the electrochemistry o~ the device, the adherence o~ the metal coating to the ceramic matrix o~ the W O97/12410 PCT~US96/15621 conductive ceramic fiber or material. Generally, the metal coating should not be attacked by the electrolyte in the device.
The thickness of the metal coating on the conductive ceramic fiber or other conductive ceramic materials similarly depends on the device in which the conductive ceramic fibers or other conductive ceramic materials are employed.
Generally, the thickness of the applied metal coating should be sufficient to provide a pore free coating. For example, lead-acid batteries which employ conductive ceramic fibers formed of Ti407 and/or Ti509 having SnO7 therein may have about a .001 inch thick coating of Pb, Sn, or Sb thereon.
Similarly, alkaline batteries such as NiCd which employ conductive ceramic fibers formed of a Ti407 and/or Ti509 matrix having Ni, Co, Cn, or NiCo alloys ther-ein may have a .001 inch thick coating of Ni thereon. In Li batteries such as LiMnO2 which employ conductive ceramic fibers formed of a Ti407 and/or Ti509 matrix having Li, Ni or Mn therein may have about a .001 inch thick coating of Cu thereon. In Ni batteries which employ conductive ceramic fibers formed of a Ti407 and/or Ti509 matrix having Ni or Co therein may have about a .001 inch thick coating of Co thereon.
Well known methods such as chemical vapor deposition, plasma spraying, laser deposition, and solution dipping may be employed to apply a metal coating onto the conductive ceramic fibers or other conductive ceramic materials, provided that that method does not attack the underlying substrate. For example, tin, lead and alloys thereof can be applied by immersion dipping to provide a coating thickness on the order of microns to mils.
In a further aspect of the invention, the conductive ceramic fibers or other conductive ceramic materials may be coated with alternating metal layers of dif~ering compositions. Useful combinations of conductive ceramic CA 02233337 l998-03-27 ~ibers or other conductive ceramic materials having metal coatings thereon are shown in Table 1.

.

Metal containing additive dispersed in FIRST METALSECOND METAL
5CER~MIC MATRIX ceramic matrixCOATING COATING
Ti407 Cu Cu NONE
Ti407 Sn Sn NONE
T i407 Pb Pb NONE
Ti407 Cu Sn Pb Ti407 Sn Pb NONE
Ti407 Ag Sn-Pb alloy --Ti407 Sb Pb -~
Ti407 W ---- __ Ti407 Ni Ni Co Ti40, Co Ni ----Ti407 Ni--Co Ni--Co Ni Ti40, Li Cu ----Ti407 Zn Cu Ti407 Pb-Sn Pb-Sn Ti407 SnO2 Pb TisOg Cu Cu NONE
Ti509 Sn Sn NONE

Ti509 Pb Pb NONE
Ti509 Cu Sn Pb Tis~s Sn Pb NONE
Ti509 Ag Sn-Pb alloy --Ti509 Sb Pb --TicOq W ---- __ W O97112410 PCT~US96/15621 Metal containing additive dispersed in FIRST METALSECOND METAL
5CERAMIC MATRIX ceramic matrixCOATING COATING
TisO9 Ni Ni Co TisOg Co Ni --Ti509 Ni-Co Ni-Co Ni Ti509 Li Cu --Ti509 Zn Cu Ti509 Pb-Sn Pb-Sn Ti50Q SnO2 Pb SiC Li Cu ZrB Li Cu Active pastes which employ conductive ceramic ~ibers or other conductive ceramic materials therein typically have about 0.1-30% o~ the active paste, pre~erably about 5-20%, as conductive ceramic ~ibers depending on the conductivity o~
the conductive ceramic ~iber composition. In an active paste, the size o~ the ~ibers is su~icient to provide uni~orm distribution o~ the ceramic ~iber material throughout the paste. Use~ul sizes o~ conductive ceramic ~ibers may vary ~rom about 2-10 microns diameter.
Examples o~ components in which conductive ceramic ~ibers or other conductive ceramic materials may be employed include the grids o~ electrodes ~or batteries. The conductive ceramic ~ibers may be present in a grid ln an amount o~ about 80 to 100 % by weight o~ the grid.
In capacitors such as double layer capacitors and ultracapacitors, materials and components which may employ conductive ceramic ~ibers or other conductive ceramic materials such as Ti407 and ~i~Og whereln the ~ibers are present CA 02233337 l998-03-27 W O 97/12410 PCT~US96/156ZI
in amounts o~ about 30 to 100% based on the total weight of the plates o~ the capacitor.
In ~uel cells, materials and components which may employ conductive ceramic ~ibers or other conductive ceramic materials and molded products such as electrodes ~ormed o~
those ~ibers or other conductive ceramic materials include H~
and ~2 electrodes.
In sensors such as ~2 gas or organic vapor sensors, materials and components which may employ conductive ceramic ~ibers or other conductive ceramic materials include electrodes.
In bipolar batteries such as lead-acid bipolar batteries, materials and components which may employ conductive ceramic ~ibers or other conductive ceramic materials include ~or example, the active material.
Conductive ceramic ~ibers or other conductive ceramic materials may be ~ormed into complex shapes suitable for use in components such as grids by known methods such as weaving, knitting, braiding, extrusion, and slip casting. The conductive ceramic ~ibers or other conductive ceramic materials may be ~ormed into porous paper-like materials by known methods. The choice o~ method depends on the porosity and strength desired in the grid. For example, a grid ~ormed by felting of a liquid slurry o~ conductive ceramic ~ibers has a surface area greater than that obtainable by processes such as weaving.
When ~orming the components by extrusion, a blend o~
conductive ceramic precursor material and a binder is ~ormed by mi xi ng. The amounts o~ conductive ceramic precursor material and binder may vary within wide limits depending on the shape to be extruded as well as the speci~ic ceramic material and binder compositions. Use~ul binder compositions include those commonly employed in the manufacture o~ extruded ceramic products. Examples o~ use~ul binders include organic binders such as polyethylene, polypropylene, stearates, celluloses such as hydroxy propyl cellulose, polyesters and the like. Typically, greater amounts o~ binder materials are employed when forming intricately shaped articles. The speci~ic amounts and composition o~ binder for use with a specific conductive ceramic precursor material to provide a blend suitable ~or extrusion can readily be determined by those skilled in the art. The extruded product then is dried and ~ired to produce the desired component such as a plaque or a bipolar electrode.
In slip casting, as is generally known in the art, a slurry o~ a conductive ceramic precursor material and a liquid vehicle such as water, optionally with an organic binder and sur~actants, is cast into a mold to provide the desired shaped article. The speci~ic amounts o~ ceramic material, organic binder and liquid vehicle can be varied depending on the density desired in the cast product. The resulting cast product is dried and ~ired by conventional techniques known in the art.
Felting o~ conductive ceramic ~ibers or other conductive ceramic materials also may be employed to produce components such as grids for use in electrochemical devices such as batterles. Felting can be per~ormed as shown in the John Badger patent directed to glass mat separators. Green ~ibers, as well as certain sintered fibers, o~ the ceramic materials may be employed in well known weaving processes to produce components such as grids which then are ~ired ~or use in electrochemical devices such as batteries.

Fiber requirements The conductive ceramic ~ibers ~or use in the invention have a diameter and a length consistent with the processing requirements o~ the paste or other component in which the conductive ceramic ~iber is to be employed. Generally, pre~erred ~ibers have lengths o~ 10 to 10,000 ~ and length to diameter ratios o~ 1 to 100. Typically, when conductive ceramic fibers are employed in active pastes, the fibers are about 0.125 inches (3,175 u) to 0.250 inches (6,350 ~) long and about 0.002 to 0.007 inches diameter. The fibers, moreover, should be capable of withstanding substantial levels of shear stress. The fibers are mixed into the active ; 5 material paste by conventional mixers.
The grid for use in an electrode of a device such as a battery or fuel cell may include varying amounts of ceramic fibers or other conductive device depending on the type of device. For example, in a lead acid battery, the current collector may be formed of about fifty percent, up to one hundred percent of conductive ceramic fiber material such as Ti407 or Ti509 having therein an oxide which is conductive, stable to sulfuric acid and capable of nucleating PbO2. Such oxides include SnO2, W03, (TiO and Ti407 and/or Ti509).
Similarly, in alkaline batteries such as NiCd, about 0.1 - 20 % conductive ceramic fibers of (TiO and (Ti407) and/or Ti407) having Ni therein may be employed.
When the ceramic fibers are formed into a grid by deposition of the fibers from a liquid slurry, the diameter of the fibers may be about 0.002-0.007 inches and have a length of about 0.125 to about 0.250 inches. Generally, the conductive ceramic fibers should be long enough to yield intersecting joints and/or span the width of the mesh size of a grid to yield a conductive pathway. Specific ~iber diameters and lengths can therefore be determined by the art skilled for a speci~ic application for a given fiber composition.
Conductive ceramic fibers may be mixed with active materlals such as PbO or PbSO4 to provide improved active material pastes. The conductive ceramic fibers are uniformly distributed throughout the active material paste to provide low resistance paths for flow of electrons between the active material particles and the grid. These low resistance paths may ~unction to reduce the internal resistance of the device W O 97/12410 PCTnUS96/lS621 in which the active material is employed, especially at low states o~ charge.
Conductive ceramic ~ibers or other conductive ceramic materials may be employed in various devices such as batteries, fuel cells, capacitors, and sensors. Batteries may be classi~ied according to the shape o~ the electrodes. These classi~ications include paste type electrodes and tubular electrodes. Paste type electrodes have a grid of lead or lead alloy, or a grid formed o~ woven, knitted, or braided conductive ceramic ~ibers. Tubular electrodes are made by inserting a cylindrical tube o~ braided ~ibers such as glass ~ibers and polyester ~ibers around a grid, and then ~illing the tube with active material. Tubular type electrodes typically are employed as positive electrodes, whereas paste type electrodes are typically positive or negative electrodes.
In accordance with the invention, it is contemplated that conductive ceramic ~ibers or other conductive ceramic materials may be employed in paste and tubular electrodes.
The conductive ceramic ~ibers or other conductive ceramic materials may be admixed with additional ~ibers and the resulting blend employed in the active paste and current collector o~ a battery. The amount o~ additional ~iber in the paste or current collector may vary depending on the physical properties desired. Use~ul blends are contemplated to include Ti~07 and/or Ti509 having SnO2, Cu, Ni, Co, and the like therein with any o~ carbon ~ibers, nickel ~ibers, stainless steel ~ibers, ole~in ~ibers such as polyethylene, polypropylene, cellulosic ~iber, polyesters such as Dacron, and composite ~ibers such as lead-coated glass ~ibers. The amount o~ additional ~ibers may vary ~rom about 1 to 30 %
based on the total weight o~ active material. These additional ~ibers may be employed to impart additional mechanical strength and corrosion resistance to components ~ormed o~ the conductive ceramic ~ibers. Examples o~ use~ul blends are given in Table II.

-Wo97112410 PCT~S96/15621 TABLE~

Ceramic Ex~mple ~u~ve Me~ 01ef~
No Fib~% Fib~% Fib~%
1 Ti~07' Ni60-20% Po1y~-~p~
30-70% 10%
2 Ti509l S~ess Po1y~lu~1~e 30-70% St~1GO-70% 10-20%

3 SnOz90% -- Po1y~ 1~e 10%

4 T~07 -- Po1y~ ~c 90% 10~/o T~07 -- Pol~ter 50-90% 10-50%

1 Ti407 intercalated with Cu therein.
Z Ti509 intercalated with Nb therein.
The conductive ceramic fibers or other conductive ceramic materials employed in the invention typically have conductivity su~icient to provide an increase in conductivity o~ the active material but yet are suf~iciently porous and provide enhanced electrochemical utilization o~ the active material. The active material paste to which the conductive ceramic ~ibers are added may in~luence the amount o~
conductive ceramic ~ibers employed therein. For instance, in a lead-acid battery where the active paste material of the cathode is PbO2 having about 5-10% conductive ceramic ~iber o~
Ti407, and/or Ti509 matrix, having about 0.5-l.8% metal containing SnO2 therein may be used in the cathode. In alkaline batteries such as Zn-MnO~ wherein the less conductive - MnO2 material is used as the active paste material, about l -30% conductive ceramic ~iber o~ matrix o~ Ti407 and/or ~i509 having Cu therein may be employed in the active material. In lithium containing batteries such as Li-MnO2, about l - lO %
conductive ceramic ~iber or other conductive ceramic materials o~ matri~ Ti407 and/or Ti509 having Cu therein may be employed.
In nickel containing batteries such as NiMH, about 1 - 10 %
conductive cera~ic ~iber o~ matrlx Ti407 and/or Ti509 having Co therein may be employed. Typically, conductive ceramic fibers may be used as the additive in the active material in amounts of about 0.1% to 40% by weight o~ active material.
The diameter and length o~ the conductive ceramic ~iber ~or use in devices such as batteries, fuel cells, sensors, and capacitors may vary according to the material and component to be ~ormed there~rom, as well as the conductivity desired in the component or paste material in which the ~iber is to be employed. The method used to make the speci~ic material or component in which the conductive ceramic fiber is employed is also a ~actor in determining the diameter and length o~ the conductive ceramic fiber.
In ~orming an active paste which includes conductive ceramic ~ibers, the ~ibers should have dimensions su~icient to be processable with the active material o~ the paste.
Typically, the size o~ the conductive ceramic ~ibers may vary ~rom about 0.125-0.250 inches long and a diameter o~ about 0.001-0.005 inches, i.e. dimensions su~icient to retain the ~ibrous ~orm within the active paste material.
Various batteries may be improved by using conductive ceramic fibers. For example, in NiCd batteries, the Ni ~oam electrode may be pasted with an active material o~ Ni(OH) 2 having about 10 % conductive ceramic ~ibers o~ Ti407 and/or Ti509 having Ni therein. In NiMH batteries, a conductive ceramic ~iber o~ Ti407 andJor Ti509 having Ni or Cu therein can be added to both the cathode o~ NiOH and anode ~ormed o~
mischmetal hydride. In NiZn batteries, a conductive ceramic ~iber o~ Ti4C7 and/or Ti509 having Cu therein may be added to a paste o~ ZnO.
Nickel electrodes also may employ conductive ceramic ~ibers by adding the ~ibers to the electrode material, principally NiOOH.

In a nickel-cadmium alkaline cell, porous nickel plates are used in both the positive and negative electrodes The active material ~or the positive and negative electrodes is contained within the nickel plates. The positive plate contains nickel hydroxide while the negative plate contains cadmium hydroxide. To ~orm improved electrodes ~or use in a Ni-Cd cell, a blend o~ NiOH, CdOH and 0.5-5% of conductive ceramic fiber o~ Ti407 and/or Ti509, each having Cu, Ni therein, is mixed with about 0.5-5% organic polymeric binder such as carboxy methylcellulose in aqueous solution su~icient to provide an active material paste.
In lithium containing batteries such as Li-AgV205, Li-CF, Li-CuO, Li-FeS, Li-FeS2, Li-I2, Li-MnO2, Li-MoS2, Li-V205, Li-SOCl2, and Li-SO2, especially use~ul ceramic conductive ~ibers include Li, Co, Cu or Ni in a ceramic matrix of Ti407 and/or Ti509. Ceramic conductive ~ibers or other conductive ceramic materials such as Ti407 or Ti409 having Co or Cu therein can be manu~actured using the viscous suspension spinning process described by Cass in Ceramic Bulletin, No. 70, pages 424-429, 1991 or by other processes described herein.
In batteries in which a lithium compound o~ lithium thermodynamic activity less than that o~ lithium metal is the anode material (one example o~ which is lithium intercalated into graphite or petroleum coke, see J. M. Tarascon and D.
Guyomard, Electrochimica Acta, 38: 1221-1231 (1992)) and the cathode material is selected ~rom the group containing AgV205, CFX, CuO, MnO2, FeS, FeS2, TiS2, MoS2, V205, SOCl2, SO2, and I2, and lithium-containing materials derived there~rom (including those cathode materials suitable ~or "rocking chair" batteries as described by Michel Armand in "Materials ~or Advanced Batteries", eds. D. W. Murphy, J. Broadhead, and B. C. H.
Steele, Plenum Press, New York, at page 160 and as described by J. M. Tarascon and D. Guyomard, Electrochimica Acta 38:
1221-1231 (1992)), ceramic conductive ~ibers may be added to the cathode material to enhance current collection.

CA 02233337 l998-03-27 W O 97/12410 PCTnUS96/15621 Especially use~ul ceramic conductive ~ibers include Ni, Co, Cu and NiCo alloy in a ceramic matrix o~ Ti40? and/or Ti509 with or without TiO. Ceramic conductive ~ibers such as Ti407-Ni, Ti509-Cu are available ~rom ACI.
While the present invention has been described with respect to various speci~ic embodiments and examples it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope o~ the ~ollowing claims.
Powders Electrically conductive ceramic powders are ~ormed ~rom the oxides o~ titanium or vanadium material that may or may not have metal containing additives and "in situ" reduction agents such as carbon, metal-containing intercalated graphite, graphite, and metal powders incorporated singly or mixtures dispersed therein. All materials ~or making electrically conductive ceramic powders are in powdery ~orm and mixed to obtain a homogeneous mixture. For enhanced ceramic matrix reactivity, it is pre~erred that the particle size o~ the powders be in the range o~ 40 to 150 microns. This powder mixture is placed in a ~urnace at 300~C to burn o~f the organics and then heated up to 1000-2000~C in a reducing atmosphere o~ hydrogen or carbon monoxide or mixtures o~ these gases. In general, the reduced powdered mixture needs to be ground up to meet the particle size requires ~or an aspect ratio o~ 1.
Chips Electrically conductive chips are made ~rom the oxides o~
titanium or vanadium material that may or may not have metal containing additives and ~in situ" reduction agents such as carbon, metal-containing graphite, graphite, and metal powders incorporated singly or mixtures dispersed therein. All materials ~or making electrically conductive ceramic chips are in powdery ~orm and mixed to obtain a homogeneous mixture. A
slip is made ~rom this mixture and used in a tape casting W O 97/12410 PCT~US96/15621 process (See Mistler, Tape Casting Chapter in Engineered Materials Handbook, Vol. 4, 1992) which makes a dried or "green" (un~ired) tape of the ceramic matrix. This dried tape is then cut into ceramic chips with a pasta or like cutting machine. The chips are then placed in a furnace in air at 300~C
to burn o~ the organics, then the ~urnace temperature is raised to 1000-2000~C ~or sintering and after this the ~urnace atmosphere, but not the temperature, is changed to a reducing gas such as hydrogen or carbon monoxide or a mixture of both gases. For some electrochemical device applications, the dried tape can be thermally processed and reduced without cutting into chips ~or use as electrodes or layers in a multilayer chip capacitor. A~ter thermally processing and reducing, the chips are roughly rectangular in size and the aspect ratio (aerodynamic de~inition (long dimension/short dimension)) is 8 or less. The hot chips are cooled in a dry, inert atmosphere and stored in a sealed container. At this point, the electrically conductive ceramic chips are ready to use.
Non-electrically conductive ceramic chips are made ~rom alumina (Al2O3) or zirconia (ZrO2) or zirconia-alumina material with no metal-containing additives or "in situ" reduction agents. All materials ~or making non-electrically conductive ceramic chips are in powdered ~orm and are mixed to obtain a homogeneous mixture. A slip is made ~rom this mixture and used in tape casting to make a dried tape o~ the ceramic matrix.
This dried tape is then cut into ceramic chips with a pasta or like cutting machine. The chips are then placed in a ~urnace in air at 300~C to burn o~f the organics, then the ~urnace temperature is raised to 1000-2000~C ~or sintering and a~ter this the ~urnace atmosphere, but not the temperature, is changed to a reducing gas such as hydrogen or carbon monoxide or a mixture o~ both gases. For some electrochemical device applications, the dried tape can be thermally processed without cutting into chips. The dried tape can then be cut into electrodes and coated with a metal or metals. ~or a CA 02233337 l998-03-27 W O97/12410 PCT~US96/15621 particular application. After thermally processing, the chips are roughly rectangular in size and the aspect ratio (aerodynamic definition (long ~im~nsion/short ~im~nsion)) is 8 or less. The hot chips are cooled in a dry, inert atmosphere and stored in sealed containers. At this point, the non-electrically conductive ceramic chips are ready to be coated,plated, or deposited with a metal or metals to make them electrically conductive and/or catalytically active.

Substrates For substrate (grids, electrodes, current collectors, separators, porous sheets, foam, honey-comb sheets, solid sheets) fabrication, the electrically conductive ceramic materials, fibers, powders and chips can be mixed with a suitable binding agent and filler and the resulting mixture molded in a ram press or extruded into the desired shape. The shape is then vitrified in a non-oxidizing atmosphere at 1000-2000~C to inhibit the oxidation of the sub-oxides of the titanium or vanadium. After this vitrification process, the cooled substrates are ready for use. The ceramic foam can be made by the Scotfoam process (Selee Corporation).

Activation of non-electrically conducting materials Since the electrically conducting ceramic fibers, powders, chips and substrates have their own intrinsic electrical conductivity developed by metal compound additives and/or by a reduction of the metal sub-oxide, it only remains for the non-electrically conducting ceramic fibers, powders, chips and substrates to be made electrically conductive. The increase in electrical conductivity for the non-electrically conductive ceramic materials as well as electrically conductive substrates is done by plating or coating or deposition of singly or a mixture thereo~ metallic d-block transition elements (Sc,Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, W O 97/12410 PCTrUS96fl5621 Pt, Au, Lanthanides (Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu) and by the addition or plating or coating or deposition singly or a mixture thereo~ selected main-group elements (In, Tl, Sn, Pb, Sb, Bi, Se, Te). All materials used should have a purity level that excludes deleterious substances ~or this process as well as the pro~ected use.
There are several metal plating, metal deposition and ceramic coating techniques that can be used to treat the non-electrically conductive material and they are as ~ollows:
(1) electroless plating ~or non-conductors using a reducing solution o~ either ~ormaldehyde or hydrazine to plate out the desired metal or metals (see Lowenheim, Electroplating, pages 387-425, 1978 and 1994 Products Finishing Directory, page 112-130); (2) thermal metal spraying (See Thorp, Chemical Engineering Progress, pages 54-57, 1991) o~ the desired metal or metals and electrically conductive ceramic; and (3) layer-by-layer deposition:ion beam sputtering and laser deposition (Beardsley, Scienti~ic American, pages 32-33, 1995 and Wasa, et al., Science and Technology o~ Thin Film Superconductors-2, pages 1-2) to deposit electrically conductive ceramic materials as de~ined in this invention, and any other method to provide suitable plating, coating or deposition o~ the desired metal. Once the non-electrically conductive ceramics have been interacted with metal, metals or electrically conductive ceramic, they are now ready ~or use

Claims (46)

1. An electrical energy device having at least one component having conductive ceramic fibers therein, said fibers having a length of about 10 to about 10,000 µ (1 µ =
10-6 m) and a length to diameter ratio of about 1 to about 20.

2. The device of claim 1 wherein said conductive ceramic fibers include a metal containing additive dispersed within said ceramic matrix.

3. The device of claim 2 wherein said device is capable of at least one of generating electrical energy or storing electrical energy.

4. The device of claim 3 wherein said device is at least one of batteries, fuel cells, capacitors, and sensors.

5. The device of claim 4 wherein said device is a battery.

6. The device of claim 5 wherein said battery is at least one of lead-acid batteries, alkaline batteries, sulfur containing batteries, lithium containing batteries, and nickel containing batteries.

7. The device of claim 2 wherein said conductive ceramic fibers have at least one metal coating thereon.

8. The device of claim 7 wherein said metal coating is substantially the same composition as said metal containing additive in said fibers.

9. The device of claim 6 wherein said battery is a lead acid battery.

10. The device of claim 6 wherein said battery is an alkaline battery.

11. The device of claim 10 wherein said alkaline battery is any of Zn-AgO2, Zn-AgO, Zn-AgNO2, Zn-Ag2PbO2, Zn-HgO, Zn-MnO2 .

12. The device of claim 11 wherein said alkaline battery includes at least one conductive ceramic fiber selected from the group of titanium suboxides and titanium superoxides.

13. The device of claim 6 wherein said sulfur containing battery is a sodium-sulfur battery.

14. The device of claim 13 wherein said sodium-sulfur battery includes at least one conductive ceramic fiber comprising TiO and an oxide selected from the group of Ti4O7, Ti5O9, copper-intercalated Ti4O7 and copper-intercalated Ti5O9.

15. The device of claim 6 wherein said device is a lithium containing battery of any of Li-AgV2O5, Li-CF, Li-CuO, Li-FeS, Li-FeS2, Li-I, Li-MnO2, Li-MoS2, Li-V2O5, Li-TiS2, Li-SOCl2, Li-SO2.

16. The device of claim 15 wherein said lithium containing battery includes at least one conductive ceramic fiber selected from the group of substoichiometric titanium and superstoichiometric titanium dioxide.

17. The device of claim 6 wherein said device is a Ni containing battery of any one of Ni-Cd, Ni-H2, Ni-Zn, Ni-MH and Ni-Fe.

18. The Ni containing battery of claim 17 wherein said battery includes at least one conductive ceramic fiber selected from the group of Ti4O7 intercalated with Cu, and Ti5O9 intercalated with Cu.

19. The device of claim 3 wherein said device is a fuel cell.

20. The device of claim 3 wherein said device includes at least one electrode having conductive ceramic fibers therein, said electrode having at least one of a current collector and active material.

21. The device of claim 20 wherein said conductive ceramic fibers are present in at least one of said current collector or said material.

22. The device of claim 19 wherein said fibers are present in said collector in an amount of about 50 to 100 % by weight of said collector.

23. The device of claim 20 wherein said fibers are present in said paste in an amount of about to % by weight of said paste.

24. The device of claim 21 wherein said matrix material is selected from the group of oxides, carbides, nitrides, and borides.

25. The device of claim 24 wherein said oxide is selected from the group of substoichiometric titanium dioxides, superstoichiometric titanium dioxides, and perovskite oxides.

26. The device of claim 25 wherein said perovskite oxide is tungsten oxide.

27. The device of claim 24 wherein said metal containing additive is selected from the group of Cu, Ni, Co, Ag, Pt, Ta, Zn, Mg, Ru, Ir, Nb, V, Sn, SnO, SnO2, Pb, Pd, Ir and alloys thereof.

28. The device of claim 27 wherein said oxide is substoichiometric titanium dioxides and said metal containing additive is selected from the group of Sn, SnO, and SnO2.

29. The device of claim 3 wherein said device is in the form of a capacitor.

30. The device of claim 29 wherein said capacitor includes conductive ceramic fiber therein.

31 The device of claim 30 wherein said conductive ceramic fibers are selected from the group of titanium suboxide and titanium superoxides.

32. The device of claim 3 wherein said sensors include at least one of thermal sensors and chemical sensors.

33. The device of claim 32 wherein said thermal sensor is in the form of single fibers or bundles of conductive, doped ceramic fibers.

34. The device of claim 33 wherein said chemical sensor is in the form of a sheet, paper, nonwoven or woven mat, and composed principally of conductive ceramic fibers.

35. A lead-acid battery having a plurality of electrodes therein, said electrode comprising an active material composition and a current collector, wherein conductive ceramic fibers are included in at least one said active material and said current collector.

36. The lead acid battery of claim 35 wherein said active material composition is lead dioxide and said conductive ceramic fibers have a substoichiometric titanium dioxide matrix and a Sn-Pb alloy dispersed throughout said matrix.

37. The lead acid battery of claim 36 wherein said current collector comprises conductive ceramic fibers from the group of substoichiometric titanium and superstoichiometric titanium.

38. The lead acid battery of claim 37 wherein said ceramic fiber comprises substoichiometric titanium dioxide having Sn-Pb alloy therein.

39. The lead acid battery of claim 38 wherein said substoichiometric titanium dioxide is Ti4O7.

40. The device of claim 5 wherein said battery comprises an anode compartment having a lithium material of thermodynamic activity less than that of lithium metal.

41. The device of claim 40 wherein said battery comprises a cathode compartment that comprises a material containing manganese.

42. The device of claim 40 wherein said battery includes an electrolyte material comprises an organic polymer.

43. The device of claim 40 wherein the lithium material is intercalated into a carbon material selected from the group containing graphite and petroleum coke.

44. The device of claim 5 wherein the battery is of bipolar design.

45. A battery which comprises an electrically conductive ceramic comprising electrically conductive vanadium oxide, wherein said conductive vanadium oxide includes therein at least one of M oxides and free metal where M is selected from the group of Cr, Cu, Ni, Pt, Ta, Zn, Mg, Ru, Ir, Nb, V, or mixtures thereof, and said vanadium oxide has the formula VOx where x is between about 1 and 2.5.

46. A battery which comprises electrically conductive ceramic fibers comprising an oxide selected from the group of Ti4O7 and Ti5O9 coated with a metal.