Classifications

• • 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
  • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• This invention relates to batteries. More specifically, this invention relates to batteries which incorporate tractable, stable, conductive polymers as the electrodes. Extensive research is being conducted into stable, light-weight, high-energy density, rechargeable, i.e., secondary, battery systems. Two major applications for such secondary batteries among others are the storage of electric energy for electric vehicle propulsion and load leveling applications for electric utilities.
• the battery technologies currently under active study suffer from a variety of drawbacks.
• Many of the new light-weight, secondary batteries under study employ materials which are spontaneously combustible or highly toxic, such as molten lithium, sodium, sulfur and the like.
• Polyacetylene is an example of an organic polymer which can be rendered conductive by suitable doping procedures.
• the conducting polymers can be used as electrodes in a battery.
• the ability to charge and discharge such polymers repeatedly provides for their use as electrodes in secondary batteries.
• the mode by which charge is incorporated into polyacetylene does not involve electrodeposition or require hazardous materials, thus making this an attractive alternative technology in principle.
• the polyacetylene material suffers from a number of drawbacks. In its charged forms, polyacetylene is not chemically stable, thus severely limiting the lifetime of any secondary battery device fabricated from this polymer. In addition, the material cannot be made in a tractable form.
• a tractable organic polymer is defined as a polymer which can be readily shaped, formed, molded, pressed, cast, etc. into desired articles from solution after the completion of the polymerization reaction of organic polymeric material or from the liquid state, i.e., either from the melt, fluid glassy state, or from solution.
• Electrochemical stability of a battery refers to the ability to hold the desired level of charge upon prolonged storage (shelf life) and after repeated charge-discharge cycles (cycle life).
• a stable, light-weight, primary or secondary battery comprising electrodes from tractable, electroactive polymers which can be fabricated either from a solution or from a melt into the desired electrode shape.
• the electrodes must be able to be charged electrochemically to produce conductive, stable electrode materials to serve as the cathode or anode of a light-weight, high-energy density, primary battery and reversibly charged to produce a secondary battery.
• the electrodes fabricated from polymers of recurring diradical repeat units whose corresponding monomeric repeat units are capable of forming stable cations or anions upon reversible electrochemical oxidation or reduction.
• a higher power density and energy density than traditional batteries is also desirable.
• these non-traditional shapes can occupy any space within the vehicle such as inside door panels, trunks, hoods, under or within seats, etc.
• the invention provides a primary or secondary battery incorporating at least one electroactive, organic polymer electrode which possesses the desirable properties previously recited.
• the electrode(s) incorporated into the battery in their simplest form comprise a current collector, such as metal wire or metal foil or any other electrical conductor, and a linear tractable electroactive polymer contacting or surrounding the current collector.
• the linear polymer is capable of undergoing a reversible oxidation or a reversible reduction or both to a charged conductive state..
• the polymer exhibits considerable stability in the charged conductive state, i.e., as an electroactive polymer.
• An electroactive polymer is defined as a polymer having a conductivity which has been modified with electron acceptor or electron donor dopants to a greater conductivity than the virgin or unmodified state of the polymer.
• the linear polymer comprises diradical repeat units selected from the group consisting of a heterocyclic ring system including at least one Group 5B or Group 6B atom (IUPAC), wherein none of the ring carbon atoms is saturated, a heterocyclic ring system including at least one Group 5B or 6B atom wherein none of the ring carbon atoms is saturated and a connecting unit, and mixtures thereof, wherein said diradical repeat unit in the form of a monomeric repeat unit is capable of undergoing reversible oxidation or reversible reduction or both to form a stable ionic species and wherein said connecting unit is a conjugated system or atom or group of atoms which maintain the IT orbital overlap with the heterocyclic ring system.
• IUPAC Group 5B or Group 6B atom
• a diradical repeat unit is defined as the smallest structural building block of the polymer backbone having two unsatisfied positions available for linking. These are utilized to propagate the backbone.
• the diradical repeat units are selected from the group consisting of a heterocyclic ring system, a heterocyclic ring system and a connecting unit, or mixtures thereof.
• the heterocyclic ring systems include at least one Group 5B or 6B atom (IUPAC System). None of the ring carbon atoms in the heterocyclic ring system is saturated. More specifically, the heteroatoms are selected from the group consisting of N, P, As, Sb, and Bi for the Group SB atoms and O, S, Se, and Te for the Group 6B atoms. N, O, S are the preferred heteroatoms.
• heteroatoms are distributed among the ring system such that when the ring system is comprised of fused rings, the heteroatoms do not occupy the ring fusion positions. Furthermore, when more than one heteroatom is selected for a mono or fused heterocyclic system, no two heteroatoms can be adjacent to one another unless the heteroatoms are both nitrogen in which case no more than two adjacent nitrogens are permitted.
• a monomeric repeat unit is defined as a diradical repeat unit wherein the unsatisfied positions are substituted by hydrogen atoms.
• the monomeric repeat unit must be capable of undergoing reversible oxidation or reversible reduction to a stable ionic species.
• a stable ionic species is defined as a charged atomic or molecular species in the condensed phase which maintains its chemical integrity throughout the course of the chemical process of interest.
• a connecting unit is defined as any atom or group of atoms which can link the heterocyclic ring systems together into a polymer chain without adversely effecting the reversible oxidation or reversible reduction of the polymer.
• the connecting unit must be conjugated or maintain the IT orbital overlap with the heterocyclic ring system.
• the tractable virgin polymers can be rendered electroactive by subjecting them to reversible electrochemical oxidation or reversible electrochemical reduction reactions. This is accomplished by immersing the virgin polymer in a suitable electrolyte solution and using the polymer as one electrode of an electrochemical cell. It is preferred that the electrolyte solution swell the polymer matrix. Upon passing of an electric current through such a cell, the polymer becomes either partially or fully reduced or oxidized (depending upon the direction of current flow) and charge-compensating cationic or anionic dopants from the supporting electrolyte become incorporated into the polymer.
• the resulting electroactive polymer is conductive and consists of a charged polymer backbone incorporating charge-compensating ionic dopants.
• the charges of the polymer and the charge-compensating ionic dopants balance so that the electroactive polymer is electrically neutral. Furthermore, the electrochemical oxidation or reduction proceeds solely by an electron transfer.
• the charge-compensating anions or cations are associated with the charged polymer backbone but do not chemically react with or modify said backbone.
• the electroactive polymer has a conductivity which is greater than the conductivity of the virgin polymer.
• the conductivity is several orders of magnitude greater than that of the virgin polymer.
• the process by which the polymer is rendered electroactive can also be used to store charge when the polymer is used as an electrode of a primary or secondary battery.
• Charge is stored in the identical procedure described above wherein the virgin polymer is either oxidized and reduced to form a charged polymer backbone with which charge-compensating anionic or cationic dopants are associated.
• the polymers of t-his invention can form either electrode of a battery.
• the polymer is a cathode when anode materials are selected which have a more negative redox potential than the polymer, such as lithium, sodium, and the like.
• the polymer is an anode when cathode materials are selected which have a less negative redox potential than the polymer, such as copper, polypyrrole, and the like.
• the voltage of the battery is determined by the difference in the individual electrode redox potentials of the electrode materials. Therefore, the anode preferably has a negative reduction potential and cathode has a positive oxidation potential.
• n-type polymers Polymers which are reversibly reduceable are known as n-type polymers. These are especially suited for use as anodes.
• An n-type electroactive organic polymer of this invention is obtained by electrochemically reducing the virgin polymer to a polyanion and incorporating into it charge-neutralizing cations.
• Polymers which are reversibly oxidizable are known as p-type polymers. These are especially suited for use as cathodes.
• a p-type electroactive organic polymer is obtained by electrochemically oxidizing the virgin polymer to a polycation and incorporating into it charge neutralizing anions.
• the polymers as electrodes are stable in their electroactive or charged states because they are composed of diradical repeat units whose monomeric repeat units form stable cations and anions, respectively, upon electrochemical oxidation or reduction. This imparts electrical stability to the battery which is fabricated therefrom.
• the energy density of a battery fabricated with these polymers as either electrode or both electrodes can be calculated from the molecular weights of the polymer and the redox potentials of the electrochemically active repeat unit. Batteries which exhibit energy densities of which are greater than 50 watt-hours/kg and preferably greater than 100 watt-hours/kg may be fabricated from the aforementioned polymers.
• the electrodes can be closely spaced and fabri cated as thin films because the polymers retain their structural and dimensional integrity during the charging and discharging cycles.
• conventional inorganic electrodes require sturdy electrode supports to provide a surface for dissolution and redeposition of the active electrode metal and require larger spacings between the electrodes to avoid short-circuiting of the battery due to uneven growth or dendritic growth of the metallic electrode materials.
• the polymer electrodes require only sufficient electrolyte solution to swell the polymers enough so that the diffusion of charge-compensating ionic dopants into and out of the polymer matrix is sufficiently high to sustain a reasonable discharge rate.
• the electrolyte ions can be present largely in the solid state as a slurry in a minimal volume of a saturated electrolyte solution between the two electrodes. These properties make it possible to achieve energy-density values which exceed those for most conventional battery technologies.
• the fact that sturdy electrode supports and large interelectrode spacings are not necessary with these polymer battery electrodes also makes it possible to increase the surface area of the electrodes substantially without adding significantly to the total weight of the battery.
• FIG. 1 illustrates a battery incorporating an electroactive polymer electrode.
• the tractable electroactive unsaturated heterocyclic ring system polymers are capable of incorporating ionic conductivity modifiers and said polymers can undergo electrochemical doping and modification. Said polymers are useful as electrode materials in batteries of this invention.
• Preferred diradical units forming said linear polymer backbone include:
• Suitable fused 6,6, 6-membered ring system polymers are fabricated with the diradicals of thianthrenes, phenoxa-thiins, phenoxazine, N-alkylphenothiazine dihydrophenazine, dialkyldihydrophenazine, dibenzodioxin, their substituted derivatives and mixtures thereof.
• the diradicals are connected through the outer carbocyclic rings or a carbocyclic ring and a nitrogen in the central ring.
• the diradicals are interspersed with connecting units such as phenylene, vinylene, dithiophenylene and 2,5-(1,3,4-oxadiazolediyl). More specifically, polymers such as poly-2,5-phenoxazine, poly-2, 5-(3, 7-dimethyl) phenoxazine, poly-2,5-(l,4-phenylene)phenoxazine, poly-
• Suitable fused 5,6-membered ring system polymers are fabricated with the diradicals of benzoxazole, benzothiazole, benzoselenazole, N-alkyl-substituted benzimidazole, their substituted derivatives, and the like.
• Particular examples are poly-2,2'-(p-phenylene)-1,1'- dimethyl-5,5'-bibenzimidazole, poly-2, 2'-(p-phenylene)- 5,5-bibenzoxazole, and poly-2,2'-(p-phenylene)-5, 5'- bibenzothiazole.
• the polymers are capable of undergoing reversible reduction and thus form stable n-type polymers.
• polymers are preferred for use as anode materials of this invention.
• Particularly preferred polymers are poly- 2,2'-(p-phenylene)-6, 6'-bibenzoxazole, poly-2, 2'-(p- phenylene)-l,l'-dimethyl-6,6'-bibenziraidazole, and poly- 2,2'-(p-phenylene)-6,6'-bibenzothiazole. These polymers are capable of undergoing a reversible oxidation and reversible reduction, i.e., n-type and p-type characteristics.
• polymers are especially preferred for use as either anode materials (i.e., when said polymer is n-type) or cathode materials (i.e., when said polymer is p-type) of this invention.
• Other preferred polymers are poly-(2,2'-(m-phenylene)-6, 6'-bibenzoxazole, poly-2, 2'- (m-phenylene)-l,l'-dimethyl-6,6'-bibenzimidazole, poly- 2,2'-(m-phenylene)-6,6'-bibenzothiazole, and poly-2,2'-(Nmethyl-p,p'-aminodiphenylene)-6, 6'-bibenzoxazole.
• These polymers are capable of undergoing reversible oxidation and thus form a stable p-type polymer.
• These polymers are preferred for use as cathode materials of this invention.
• Suitable 5, 6, 5-membered ring system polymers are fabricated with the diradicals of 1,7-dialkyl-benzo[1,2- d:4,5-d'] diimidazoles, such as 1,7-dimethyl-benzo [1,2,- d:4,5-d'] diimidazole; benzo [1,2-d:5,4-d']bisthiazole; benzo [1,2-d:4,5-d']bisthiazole; benzo [1,2-d:4,5-d']bisselenazole; benzo [1,2-d:4,5-d'] bisselenazole; benzo[1,2- d:4,5-d']bistellurazole; selenazolo[5,4-f] benzothiazole; 1,8-dialkyl-benzo [1,2-d:3,4-d']diimidazoles, such as 1,8- dialkyl-benzo [1,2-d:3,4-d']diimidazole; benzo [1,2-d:5,4-
• poly-2,6-(p-phenylene)-benzo[1,2-d:5,4-d']bisoxazole poly-2,6-( ⁇ -phenylene)-1,7-dimethyl-benzo [1, 2- d:4,5-d']diimidazole
• poly-2, 6-(p-phenylene)-benzo [1,2- d:4,5-d'] bisthiazole poly-2,6-(m-phenylene) benzo [1,2- d:4,5-d"] bisthiazole.
• Preferred polymers exhibit n-type properties.
• Suitable monocyclic heterocyclic ring system polymers are comprised from recurring diradicals of triazoles, heterodiazoles such as thiadiazole, oxadiazole, and the like, and heteroazoles such as oxazole and thiazole, all said monocyclic heterocyclic systems incorporating 1,4-phenylene as a connecting unit. Optionally these systems may incorporate other preferred connecting units.
• Suitable polymers are poly-1,4- phenylene-2, 5-(1, 3, 4-oxadiazole), copolymer of oxadiazble and thiadiazole, poly-1,4- phenylene-2,5-(1,3,4-thiadiazole), ⁇ oly-4,4'-N- methylaminodiphenylene-2, 5-(1,3,4-oxadiazole), poly-1, 4- phenylene-2,4-(1,3-thiazole), poly-l,4-phenylene-2,5-(1- phenyl-1,3,4-triazole), and poly-l,4- ⁇ henylene-2,5-(1,4- dithiin).
• Preferred polymers exhibit n-type characteristics.
• polymers are preferred for use as anode materials of this invention.
• monocyclic systems only those compounds whose corresponding monomeric repeat units are able to undergo reversible reduction or reversi ble oxidation to a stable ionic species are within the scope of the invention.
• any of the above mono or fused heterocyclic systems can be substituted with one or more substituents as long as the ring carbon atoms remain unsaturated.
• suitable polymers are composed of recurring diradical units of fused, 6,6-membered, nitrogen-containing, heterocyclic ring systems.
• the fused rings contains from 1 through 6 nitrogen atoms and preferably 1-4 nitrogen atoms.
• the nitrogen atoms are distributed between the fused rings with 2 or less nitrogens bonded sequentially in a ring and none of the nitrogens occupying the ring fusion positions. These polymers exhibit n-type characteristics and are preferred for use as anode materials of this invention.
• Suitable examples of single-nitrogen, fused-ring systems are any of the diradicals of quinoline and isoquinoline. Preferred quinoline polymers exhibit n-type conductivity.
• Suitable examples of two-nitrogen, fusedring systems are any of the diradicals of cinnoline; quinazoline; quinoxaline; 2-phenylquinoxaline; phthalazine; 1,5-naphthyridine; 1,6-naphthyridine; 1, 7- naphthyridine; 1,8-naphthyridine; 2,6-naphthyridine; copyrine; and the like.
• Suitable examples of threenitrogen, fused-ring systems are any of the diradicals of 1,2,4-benzotriazine; pyrido [3,2-d]pyrimidine; pyrido[4,3- djpyrimidine; pyrido [3, 4-d]pyrimidine; pyrido [2,3- djpyrimidine; pyrido [2, 3-b]pyrazine; pyrido[3,4- b]pyrazine; pyrido(2, 3-d] pyridazine; pyrido [3, 4- d]pyridazine; and the like.
• Suitable examples of fournitrogen, fused-ring systems are any of the diradicals of pyridazino [4, 5-c] pyridazine; pyrimido [5, 4-d] pyrimidine; pteridine; pyrimido [4,5-d] pyridazine; pyrimido [4, 5- djpyrimidine; pyrazino [2, 3-b]pyrazine; pyrazino [2, 3- d]pyridazine; pyridazino [4, 5-d]pyridazine; pyrimido [4,5- c]pyridazine; pyrazino [2,3-c]pyridazine; pyrido [3, 2-d]-astriazine; pyrido [2,3-e]-as-triazine; and the like.
• Suitable examples of five-nitrogen, fused-rihg systems are any of the diradicals of pyrimido [4 ,5-e]-as-triazine; pyrimido [5,4-d]-as-triazine; and the like.
• Suitable examples of six-nitrogen, fused-ring systems are any of the diradicals of as-triazino [6,5-d]-as-triazine; and the like. All the previously mentioned fused, nitrogen-ring systems are known and disclosed in The Ring Index, 2nd Edition, and Supplements I, II and III, Patterson et al, American Chemical Society. These polymers are preferred for use as anode materials of this invention.
• the molecules are synthesized into polymers by methods known in the art such as treatment with ZnCl2 or FeCl 3 and an alkyliodide, or by dichlorination followed by reaction with appropriately disubstituted molecules such as: disodiura sulfide, disodium salt of ethylene glycol, and the like.
• the diradicals can .be modified with substituents such as electron donating or withdrawing groups by methods known in the art which modify the polymer properties.
• the diradicals can also be separated by one or more connecting units. Preferred connecting units are phenylene,
• Suitable polymers in which the nitrogens of the diradicals are in the ionic form include N-alkyl quinolinium and the like for the above compounds.
• the electroactive polymers of the invention have the following formula:
• the repeat units form the polyanion or polycation of the electroactive polymer.
• the diradical R group is a substituted or unsubstituted heterocyclic systems previously recited.
• quinoline, isoquinoline, substituted derivatives, or mixtures thereof are preferred.
• Preferred quinoline polymers have the diradicals connected at the 2,6 and 3,6 positions. Substitution in the 4 position is preferred such as poly-2,6-(4-phenylquinoline).
• Another preferred polymer is composed of quinoxaline units, substituted quinoxaline, or mixtures thereof.
• the diradicals can be separated by one or more X or Y connecting units which are an atom or group of atoms capable of linking the diradicals into the polymer chain.
• R 1 is lower alkyl C 1 -C 6 , aryl, and cycloalkyl, and R v , R vi and R vii are H or methyl, methoxy, halogen and mixtures thereof;
• R 2 is lower alkyl C 1 -C 4 and p-substituted phenyl; and
• Ar is phenylene or biphenylene.
• connecting units are phenylene, -o-, -s-, biphenylene,
• electroactive n-type polymers which are substituted and/or incorporated connecting units. These are preferred for use as anode materials of this invention.
• a preferred polymer has the formula:
• Another preferred polymer has the formula:
• Another preferred polymer has the formula:
• Another preferred polymer has the formula:
• Z is a connecting unit
• R and R' are quinoline diradicals with a substituent group R iii in the 4 position selected from the group consisting of K, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms, a cycloaliphatic group of 5 or 6 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkenyl groups of 2 to 4 carbon atoms, alkynyl groups of 2 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthiol of 1 to 4 carbon atoms, a 5- or 6-member
• Still another preferred polymer is when R iii is phenyl and
• R vii is H.
• a preferred polymer of poly(phenylquinoxaline) has the formula:
• FIG. 1 illustrates a primary or secondary battery 10.
• the battery 10 has a case 12 which contains the anode 14 and the cathode 16 separated by a separator 18.
• the battery is charged by reducing the anode and oxidizing the cathode while the electrodes 14 and 16 are immersed in a supporting electrolyte dissolved in a solvent.
• the supporting electrolyte refers to a salt or other cation-anion couple, dissolved in a suitable solvent.
• the supporting electrolyte and the solvent are referred to as the electrolyte 20.
• Wires 24 and 22 connect to the anode 14 and cathode 16, respectively, for charging and discharging the battery 10.
• the electrodes 14 or 16 are fabricated from polymers, the electrodes 14 and 16 are fabricated over or contacting a current collector, not shown, such as a platinum wire or foil, or other suitable low-resistance, conductive material which does not adversely react with the polymer. Materials such as carbon felt, graphite, vitreous carbon, platinum, gold, nickel, and the like are also suitable.
• the current collector has a conductivity of about 100 ohm -1 cm -1 , or greater.
• the heterocyclic ring system polymers can be used as either the anode 14 or cathode 16.
• n-type polymers are used as anodes and p-type polymers are used as cathodes.
• the anode 14 comprises a polymer such as poly-2,6-quinoline or poly-2, 6-(4- phenylquinoline),.
• polymers such as poly-2,5- phenoxazine, poly-3, 7-(N-methylphenothiazine)-2, 5-(1, 3,4- oxadiazole), poly-2, 2-(m-phenylene)-6, 6'-bibenzoxazole, and the like, all being p-type polymers in their electroactive forms, comprise the cathode 16.
• the batteries of this invention can comprise p-type heterocyclic polymers as cathodes and alkali metals such as lithium, sodium, and the like as the anode.
• alkali metals such as lithium, sodium, and the like
• Another preferred embodiment of this invention comprises the use of n-type heterocyclic polymers as anodes and materials, whose redox potentials are more positive than the redox potentials of the said n-type heterocyclic polymers, can serve as cathodes.
• materials such as Ag, Fe, or other polymeric materials such as polyacetylene or polypyrrole can be utilized as cathodes.
• Yet another preferred embodiment of this invention regards the use of n-type heterocyclic polymers as cathodes and materials, whose redox potential is more negative than the redox potential of the said n-type heterocyclic polymers, can serve as anodes.
• poly- 2,6-(4-ph.enylquinoline) or poly-2, 6-(4-phenyl)-N- methylquinolinium can be the cathodes and alkali metals such as lithium and sodium and the like can be the anodes.
• the anode 14 is preferably fabricated from n-type polymers such as poly-2,6-quinoline, poly-2, 6-(4- phenylquinoline), polyquinoxaline, their substituted derivatives, and the like, the anode is charged by electrochemically reducing, i.e., negatively charging, the poly- quinoline in the presence of supporting electrolyte cations dissolved in a solvent. The cations associate with the charged polymer.
• the cathode 16 when the cathode 16 is fabricated from p-type polymers such as poly-2,5- phenoxazine, poly-3,7-(N-methylphenothiazine)-2,5-(1, 3, 4- oxadiazole), poly-2, 2'-(m-phenylene)-6, 6'-bibenzoxazole, their substituted derivatives, and the like, the cathode is charged by electrochemically oxidizing, i.e., positive charging, said polymers in the presence of supporting electrolyte anions dissolved in a solvent. The anions associate with the charged polymer.
• electrochemically oxidizing i.e., positive charging
• Suitable electrolyte cations are selected from cations such' as Li + , Na + , K + , Cs + , Mg ++ , (CH 3 ) 4 N + , (C 2 H 5 ) 4 N + , (C 3 H 7 ) 4 N + , and (C 4 H 9 ) 4 N + , and the like as disclosed in French Patent Publication No, 2,505,854, published November 19, 1982.
• the cation can be any cation, the salt of which can be dis ⁇ solved in the solvent and will not adversely react with the electrode materials.
• Suitable electrolyte anions can be F-, Cl-, Br-, C10 4 -, BF 4 -, NO3-, PF 6 -, AsF 6 -, and the like. Mixtures of salts can be employed.
• the cathode 16 can be any material which can be oxidized during the charging of the battery and will not adversely react with the anode.
• Suitable examples of cathode materials include silver coated with a silver halide such as AgBr, AgCl, or Agl; polymers such as polyacetylene, polypyrrole, polyphenylene sulfide, polyphenylene, or poly-1,6-heptadiene; other p-type heterocyclic polymers; or an intercalation compound having a redox potential which is more positive than the redox potential of the anode.
• An intercalation electrode is defined as an electrode material having a host lattice structure, [Z] , which participates in an electrochemical reaction via an intercalation mechanism to yield an intercalation compound:
• Li x TiS 2 is an example of a suitable intercalation compound cathode material. Li x TiS 2 has a reported redox potential of about -0.8 volts.
• intercalation compounds are the chalcogenides of Group IV-B such as TiS 2 , TiSe 2 ; Group V-B metals such as V 2 S 5 , V 2 Se 4.5 , (NH 4 ) 3 VS 4 ; Group VI-B metals such as (NH 4 ) 2 MoSe 2 ; and Group VIII metals such as FeS, FeS 2 , CoS, CoS 2 , NiS, NiS2; and the like.
• Group IV-B such as TiS 2 , TiSe 2
• Group V-B metals such as V 2 S 5 , V 2 Se 4.5 , (NH 4 ) 3 VS 4
• Group VI-B metals such as (NH 4 ) 2 MoSe 2
• Group VIII metals such as FeS, FeS 2 , CoS, CoS 2 , NiS, NiS2; and the like.
• the cathode can also be a salt form of the polymer or an N-alkylated form of the polymer such as poly-2,6-(4-phenyl)-N-methylquinolinum with an anion.
• Suitable ions are Cl- t Br-, F-, I-, BF 4 -, C10 4 -, PF 6 -, AsFg-, N0 3 -, and the like.
• the cathode can be a polypyrrole material, PP y , as taught by A. F. Diaz, J. C. S. Chem. Com. , 1979, pp. 635-636, Host preferably, the cathodes are any p-type heterocyclic polymers previously recited. If the cathode is polypyrrole (PPy) with an electrolyte solvent of acetonitrile with the supporting electrolyte of tetrabutylammonium-tetrafluoroborate dissolved therein, the charging of the PP y in the battery is illustrated as follows:
• the separator 18 need only prohibit electrical shorting between the anode and cathode.
• a suitable example would be a fine-mesh nylon grid. Any separator can be used in the invention so long as it is an electrical insulator and is not soluble in the electrolyte solution and does not prevent the free flow of ions. Another example would be a teflon grid.
• the separator must be an ion selective membrane if a supporting electrolyte or counter electrode is selected which chemically reacts with the polymer electrode. The ion-selective separation would divide the battery 10 into an anode compartment and a cathode compartment.
• an ion-selective sepa rator is required when the anode is PPQ and the cathode is Ag, Fe, Cu, Zn, Ni, Pd, Sn, or other metal which could plate out onto the anode.
• the solvent portion of electrolyte 20 can comprise any liquid which dissolves the supporting electrolyte into its ionic form.
• Suitable solvents can be any material which would not dissolve the electrode, case, or separator such as acetonitrile, propylene carbonate, tetrahydrofuran, propionitrile, butyronitrile, phenyl acetonitrile, dimethylforamide, dimethoxyethane, dimethyl sulfoxide, pyridine, or mixtures thereof, and the like.
• Any gelling agents known in the art which are suitable for increasing the viscosity of the supporting electrolyte without inhibiting the dissociation of the supporting electrolyte or movement of ions therethrough are suitable, for example, starch, guar gum, and the like.
• the output voltage of the battery is determined by the difference between the redox potential of the anode material and the redox potential of the cathode material.
• poly-2,6-(4-phenylquinoline) reduces at a potential of about -2 volts vs. the Standard Calomel Electrode (SCE), i.e., a redox potential of about -2.0 volts.
• SCE Standard Calomel Electrode
• Polypyrrole oxidizes at a potential of about o volts vs. SCE.
• a single-cell battery is constructed using these two polymers as the anode and cathode, respectively, a nylon mesh grid separator between the electrodes, and an electrolyte solution of tetraethylammoniumtetrafluoroborate dissolved in acetonitrile, then the output voltage of the resulting cell is about 2 volts. This compares to the voltage of a single-cell lead/lead oxide-acid battery.
• the series connection of 6 cells of the battery would provide a standard 12-volt system as used in automobiles and the like. Any number of cells could be connected in parallel to obtain the necessary and desired output current.
• the polymer is paired with an electrode material having a more negative redox potential than the polymer.
• the polymer functions as a cathode.
• Suitable materials with more negative redox potentials which can function as the anode are metals such as Li, Na, K, Rb, Cs, or an alloy thereof.
• the anode can also be an intercalation compound having a more negative redox potential than the polymer cathode such as Li x W0 2 .
• Li x W0 2 has a redox potential of about -2.5 volts.
• a battery can be fabricated with a PPQ cathode and Li anode.
• the PPQ cathode is reduced, i.e., negatively charged, and doped with the cationic portion of a lithium containing electrolyte salt, such as lithium perchlorate dissolved in propylene carbonate.
• the lithium anode is electrochemically oxidized.
• the cathode can be electrochemically oxidized, i.e., positively charged, and doped with the anionic portion of a lithium-containing electrolyte salt such as lithium perchlorate dissolved in propyl ene carbonate.
• the cathode reaction can be illustrated as follows:
• the anode reaction can be illustrated as follows:
• the use of the previously recited heterocyclic polymers in the construction of the anode and/or cathode represents a significant improvement in the electrochemical stability of the resulting battery over that attained with polyacetylene and other conductive polymer materials reported to date.
• the distinguishing feature of polymers of this invention which provides for this improvement is the fact that they are composed of diradical repeat units, whose corresponding monomeric repeat units form stable cations or anions, respectively, upon reversible electrochemical oxidation or reduction.
• the battery can undergo repeated deep discharging.
• the battery exhibits an extremely high discharging rate corresponding to a peak power density of about 12 kw/lb.
• the depth of discharge and charge is almost 100%. In 60 cycles of deep charging and. discharging, th.e battery exhibits no appreciable change in its characteristics.
• the battery is not limited to the construction illustrated in the figure.
• the battery may be fabricated in a cylindrical shape wherein alternating layers of polyquinoline anode, a separator incorporating an electrolyte, a cathode such as poly-2, 2'-(m-phenylene)-bibenzoxazole, are rolled in a spiral configuration, as seen from a cross-section, and are tubular in length. Any number of alternating layers of anode and cathode materials separated by a separator can be employed to increase the charge storage capacity and power output of the battery. Having described the electrolytes, the battery and the methods of fabrication of the battery, the following examples are intended to be illustrative of the invention and not meant to limit the scope thereof.
• a platinum/poly-2,6-(4-phenylquinoline)/ tetrabutylammonium-bromide, acetonitrile/silver bromide/ silver battery was fabricated in which the poly-2,6-(4- phenylquinoline) served as the anode material and the silver/silver bromide as the cathode material.
• a 10 cm length of silver wire was anodized in an acetonitrile solution of Bu 4 NBr, passing about 20 coulombs of charge to form an AgBr layer.
• a platinum wire was coated with a thin film of poly-2,6-(4-phenylquinoline) by immersing the wire in 5% meta-cresol/P 2 O 5 solution of the polymer, followed by a neutralization in an ethanol/triethylamine bath.
• the resulting film was a few microns in thickness.
• the two electrodes were immersed in a one-molar solution of Bu 4 NBr in acetonitrile and arranged so as to not touch each other.
• the cell was charged by connecting the electrodes to a 2.7-volt dry cell for a few minutes.
• the resulting battery exhibited an open-circuit voltage of 0.75 volts and a short-circuit current of 340 microamps, corresponding to a current density of 3.5 milliamps per square centimeter.
• Example 2 A platinum/poly-2,6-(4-phenylquinoline)/ tetraethylammonium-tetrafluoroborate, acetonitrile/ polypyrrole/platinum battery was fabricated in which the poly-2,6-(4-phenylquinoline) served as the anode material and the polypyrrole as the cathode material. A polypyrrole film was electrodeposited on a 10 cm 2 area platinum foil electrode according to the published procedures of
• the electrodes were separated with a nylon mesh.
• the cell was charged with a 2.7-volt dry cell in a period of a few minutes.
• the resulting battery exhibited an open-circuit voltage of 2 volts and a short-circuit current of 250 milliamps, corresponding to a current density of about 12 milliamps per square centimeter.
• the discharged battery was recharged by connecting it to an external 2.7-volt dry cell for a period of a few minutes. Over 100 charge-discharge cycles were performed in this manner with no change in open-circuit voltage, short-circuit current or battery capacity.
• Example 3 A lithium/lithium perchlorate, propylene carbonate/poly-2,6-(4-phenylquinoline)/platinum battery was fabricated in which the poly-2,6-(4-phenylquinoline) served as the cathode material and the lithium served as the anode material.
• a lithium anode was prepared by electrodepositing a fresh lithium coating onto a 20 cm platinum-foil electrode from a solution of LiC10 4 in propylene carbonate, passing a total of -58 coulombs of charge.
• a similar platinum-foil electrode was coated with a thin film of poly-2,6-(4-phenylquinoline) as in
• Example 1 The battery was assembled by immersing the two electrodes face to face in a solution of LiC1O 4 in propylene carbonate and separating them with a nylon mesh screen to avoid shorting.
• the open-circuit voltage of the battery was 2.37 volts with a short-circuit current of 95 milliamps corresponding to a current density of 5 milliamps per square centimeter.
• the discharged battery was recharged by connecting it to an external 2.7-volt dry cell for a period of about one minute. Subsequent charge-discharge cycles were carried out with similar results, but showing a gradual lowering of the capacity of the battery.
• Example 4 A carbon/poly-2, 6- (4-phenylquinoline)/ tetraethylammonium-tetrafluoroborate, acetonitrile/ poly-2,5-phenoxazine/carbon battery was fabricated in which the poly-2,6-(4-phenylquinoline) served as the active anode material and the poly-2,5-phenoxazine served as the active cathode material.
• a reticulated vitreous carbon block was coated with poly-2,6-(4-phenylquin ⁇ line) by immersion in a 5% meta-cresol/P 2 O 5 solution of the polymer, followed by neutralization in an ethanol/ triethylamine bath.
• a second reticulated vitreous carbon block was coated with the phenoxazine polymer by electrochemically oxidizing a THF solution of the polymer, resulting in an electrodeposited oxidized poly-2,5- phenoxazine film.
• the electrode was then rinsed with THF and dried in an inert atmosphere.
• the electrode was then immersed in a 0.1-molar solution of tetraethylammoniumtetrafluoroborate in acetonitrile and electrochemically reduced to yield a neutralized vitreous carbon electrode coated with a thin film of neutral poly-2,5-phenoxazine.
• the two coated carbon anode and cathode electrodes were immersed in a 0.5-molar tetraethylammonium tetrafluoroborate solution in acetonitrile and separated with a thin nylon mesh.
• the battery was charged with two 1.5-volt dry cells to give an open-circuit voltage of 3.0 volts at full, charge.
• the short-circuit discharge of this cell showed a current plateau of about 125 milliamps for most of the discharge, followed by a precipitous drop in the current near full discharge.
• the cell was then recharged with the dry cells, yielding a 3.0-volt open circuit voltage and an identical response upon short- circuit discharge.
• Example 5 A platinum/poly-2,6 - (4-phenylquinoline)/ tetraethylammonium-tetrafluoroborate, acetonitrile/poly- [2,6-(N-methyl-4-phenyl) quinolinium]/platinum battery was fabricated in which the poly-2, 6-(4-phenylquinoline) served as the active anode material and the poly-[2,6-(N-methyl- 4-phenyl)quinolinium] served as the active cathode material. Two platinum wires were coated with poly-2,6-(4- phenylquinoline) as described in Example 1.
• the reference and auxiliary electrodes were removed from the solution so that only the two polymer-coated wires remained,
• the charged battery thus assembled exhibited an open-circuit voltage of 1.0 volts.
• the cell was then discharged at short circuit, and subsequently recharged with a 1.2-volt dry cell.
• the battery was charged and discharged in this way several times yielding an open- circuit voltage of 1.0 volts each time.
• the coulomb efficiency of the charge/discharge process was 80%.
• the battery was repeatedly recharged to 100% of its initial capacity.
• Example 6 A platinum/poly-2, 2'-(p-phenylene)-6, 6' - bibenzoxazole/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2,5-phenoxazine/platinum battery was fabricated in which the poly-2, 2'-(p-phenylene)-6, 6'- bibenzoxazole served as the active anode material, and the poly-2,5-phenoxazine served as the active cathode material.
• a platinum wire was coated with a thin film of the bibenzoxazole polymer by immersing the wire in a 5% methanesulfonic acid solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a 1 square centimeter platinum flag was coated with a thin film of poly-2,5-phenoxazine by electrochemically oxidizing a solution of the polymer in tetrahydrofuran, resulting in an oxidized, electrodeposited film. This electrode was then rinsed in tetrahydrofuran and dried in an inert atmosphere.
• the electrode was then immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile and electrochemically reduced to yield a platinum flag coated with a neutral film of poly-2,5- phenoxazine.
• the bibenzoxazole polymer-coated wire anode and the phenoxazine polymer-coated platinum flag cathode were both immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 3.5-volt dry cell.
• the charged battery exhibited an open-circuit voltage of 3.0 volts.
• the cell was then discharged at short circuit and subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open- circuit voltage of 3.0 volts each time.
• the coulomb efficiency of the charge/discharge process was 80%. Within experimental error, the battery was repeatedly recharged to 100% of its initial capacity.
• Example 7 A platinum/poly-2, 6-(p-phenylene)-benzo [1,2- d:5,4-d']bisoxazole/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2,5-phenoxazine/platinum battery was fabricated in which the benzobisoxazole polymer served as the active anode material, and the phenoxazine polymer served as the active cathode material.
• a platinum wire was coated with a thin film of the benzobisoxazole polymer by immersing the wire in a 5% methanesulfonic acid solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a 1 square centimeter platinum flag was coated with a thin film of poly-2,5- phenoxazine by electrochemically oxidizing a solution of the polymer in tetrahydrofuran, 'resulting in an oxidized, electrodeposited film.
• This electrode was then rinsed in tetrahydrofuran and dried in an inert atmosphere. The electrode was then immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile and electrochemically reduced to yield a platinum flag coated with a neutral film of poly-2, 5-phenoxazine.
• the benzobisoxazole polymer-coated anode wire and the phenoxazine polymer-coated cathode platinum flag were both immersed in a 0.1-molar solution of tetraethylammonium tetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 3.5-volt dry cell.
• the charged battery exhibited an open-circuit voltage of 3.1 volts.
• the cell was then discharged at. short circuit and subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open-circuit voltage of 3.1 volts each time. Within experimental error, the battery was repeatedly recharged to 65% of its initial capacity.
• a ⁇ latinum/poly-2, 6-(p-phenylene)-benzo [1,2- d:4,5-d']bisthiazole/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2,5-phenoxazine/platinum battery was fabricated in which the benzobisthiazole polymer served as the active anode material, and the phenoxazine polymer served as the active cathode material.
• a platinum wire was coated with a thin film of the benzobisthiazole polymer by immersing the wire in a 5% methanesulfonic acid solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a 1 square centimeter platinum flag was coated with a thin film of poly-2,5- phenoxazine by electrochemically oxidizing a solution of the polymer in tetrahydrofuran, resulting in an oxidized, electrodeposited film.
• This electrode was then rinsed in tetrahydrofuran and dried in an inert atmosphere. The electrode was then immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile and electrochemically reduced to yield a platinum flag coated with a neutral film of polyphenoxazine.
• the benzobisthiazole polymer-coated wire anode and the phenoxazine polymer-coated platinum flag cathode were both immersed in a 0.1-molar solution of tetraethylammonium tetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 3.5-volt dry cell.
• the charged battery exhibited an open-circuit voltage of 3.4 volts.
• the cell was then discharged at short circuit and subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open-circuit voltage of 3.4 volts each time. Within experimental error, the battery was repeatedly recharged to 97% of its initial capacity.
• Example 9 A platinum/poly-p-phenylene-2,5-(1,3,4- oxadiazole/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2,5-phenoxazine/platinum battery was fabricated in which the poly-p-phenylene-2,5-(1,3,4- oxadiazole) served as the active anode material, and the poly-2,5-phenoxazine served as the active cathode material.
• a platinum wire was coated with a thin film of poly-p-phenylene-2,5-(1,3,4-6xadiazole) by immersing the wire in a 5% sulfuric acid solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a 1 square centimeter platinum flag was coated with a thin film of poly-2,5-phenoxazine by electrochemically oxidizing a solution of the polymer in tetrahydrofuran, resulting in an oxidized, electrodeposited film. This electrode was then rinsed in tetrahydrofuran and dried in an inert atmosphere.
• the electrode was then immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile and electrochemically reduced to yield a platinum flag coated with a neutral film of poly-2,5- phenoxazine.
• the oxadiazole polymer-coated wire anode and the phenoxazine polymer-coated platinum flag cathode were both immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 3.5-volt dry cell.
• the charged battery exhibited an open-circuit voltage of 3.4 volts.
• the cell was then discharged at short circuit and subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open- circuit voltage of 3.4 volts each time Within experimental error, the battery was repeatedly recharged to 99% of its initial capacity.
• Example 10 A platinum/poly-2, 6-(p-phenylene)-benzo [1, 2- d:4,5-d']bisthiazole/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2, 2'-(m-phenylene)-6, 6'-bibenzoxazole/ platinum battery was fabricated in which the benzobisthiazole polymer served as the active anode material, and the poly-2, 2'-(m-phenylene)-6,6'-bibenzoxazole served as the active cathode material.
• a platinum wire was coated with a thin film of the benzobisthiazole polymer by immersing the wire in a 5% methanesulfonic acid solution of the polymer, followed by neutralization in an ethanol/ triethylamine bath.
• a second platinum wire was coated with a thin film of the bibenzoxazole polymer in a similar manner.
• the benzobisthiazole polymer-coated wire anode and bibenzoxazole polymer-coated wire cathode were immersed in a 0.1-molar solution of tetraethylammoniumtetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 4.2-volt dry cell.
• the charged battery exhibited an open-circuit voltage of 4.0 volts.
• the cell was then discharged at short circuit and subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open-circuit voltage of 4.0 volts each time.
• Example 11 A platinum/poly-2,6-(4-phenylquinoline)/ tetraethylammonium-tetrafluoroborate, acetonitrile/poly-
• 2,2'-(m-phenylene)-6,6'-bibenzoxazole/platinum battery was fabricated in which the poly-2,6-(4-phenylquinoline) polymer served as the active anode material, and the bibenzoxazole polymer served as the active cathode material.
• a platinum wire was coated with a thin film of poly-2,6-(4-phenylquinoline) by immersing the wire in a 5% meta-cresol/P 2 O 5 solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a second platinum wire was coated with a thin film of the bibenzoxazole polymer in the manner described in Example 6.
• the quinoline polymer-coated wire anode and the bibenzoxazole polymer-coated wire cathode were immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 4.2-volt dry cell.
• the charged battery exhibited an open- circuit voltage of 3.8 volts.
• the cell was then discharged at short circuit and. subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open-circuit voltage of 3.8 volts each time.
• Example 12 A platinum/poly-p-phenylene-2,5-(1,3,4- oxadiazole)/tetraethylammonium-tetrafluoroborate, acetonitrile/poly(N-methylphenothiazine)-2, 5-(1,3,4- oxadiazole)/platinum battery was fabricated in which the poly-p-phenylene-2,5-(1,3,4-oxadiazole) served as the active anode material, and the poly(N-methylphenothiazine)-2,5-(1, 3, 4-oxadiazole) served as the active cathode material.
• a platinum wire was coated with a thin film of poly-p-phenylene-2,5-(1,3,4-oxadiazole) by immersing the wire in a 5% sulfuric acid solution of the polymer, followed by neutralization in an ethanol/ triethylamine bath:
• a second platinum wire was coated with a thin film of poly(N-methylphenothiazine)-2,5- (1,3,4-oxadiazole) in a similar manner. Both polymer coated wire anode and cathode were immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile. The resulting battery was charged with a
• Example 13 A platinum/poly-p-phenylene-2, 5-(1,3,4- oxadiazole)-p-phenylene-2, 5-(1,3,4-thiadiazole) copolymer/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2, 2'-(m-phenylene)-6, 6'-bibenzoxazole/ platinum battery was fabricated in which the poly-pphenylene-2, 5-(1,3,4-oxadiazole)-p-phenylene-2, 5- (1,3,4-thiadiazole) copolymer served as the active anode material, and the bibenzoxazole polymer served as the active cathode material.
• a platinum wire was coated with a thin film of the copolymer by immersing the wire in a 5% sulfuric acid solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a second platinum wire was coated with a thin film of the bibenzoxazole polymer in the manner described in Example 10. Both polymer-coated wire anode and cathode were immersed in a 0.1-molar solution of tetraethylammonium tetrafluoroborate in acetonitrile. The resulting battery was charged with a 4.0-volt dry cell. The charged battery exhibited an open-circuit voltage of 3.5 volts. The cell was then discharged at short circuit and subsequently recharged.
• Example 14 A platinum/poly-2,6-(4-phenylquinoline)/ tetraethylammonium-tetrafluoroborate, acetonitrile/poly-
• 2,2'-(p-phenylene)-6,6'-bibenzoxazole/platinum battery was fabricated in which the poly-2,6-(4-phenylquinoline) served as the active anode material, and the poly-2,2'-(pphenylene)-6,6'-bibenzoxazole served as the active cathode material.
• a platinum wire was coated with a thin film of poly-2,6-(4-phenylquinoline) by immersing the wire in a 5% meta-cresol/P 2 O 5 solution of the polymer, followed by neutralization in an ethanol/triethylamine bath.
• a second platinum wire was coated with a thin film of the bibenzoxaz'ole polymer in the manner described in Example 6.
• Both polymer-coated wire anode and cathode were immersed in a 0.1-molar solution of tetraethylammonium tetrafluoroborate in acetonitrile.
• the resulting battery was charged with a 3.5-volt dry cell.
• the charged battery exhibited an open-circuit voltage of 3.1 volts.
• the cell was then discharged at short circuit and subsequently recharged.
• the battery was charged and discharged in this way several times yielding an open-circuit voltage of 3.1 volts each time.
• the coulomb efficiency of the charge/discharge process was 30%. Within experimental error, the battery was repeatedly recharged to 30% of its initial capacity.
• Example 15 A platinum/poly-2,2'-(p-phenylene)-6, 6'- bibenzoxazole/tetraethylammonium-tetrafluoroborate, acetonitrile/poly-2, 2'-(p-phenylene)-6, 6'-bibenzoxazole/ platinum battery was fabricated in which the poly-2,2'- (p-phenylene)-6,6'-bibenzoxazole served as both the active anode material and the active cathode material.
• Two platinum wires were coated with a thin film of the bibenzoxazole polymer by immersing the wires in a 5% methanesulfuric acid solution of the polymer, followed by neutralization in an ethanol/triethylamine bath. Both polymer-coated wire anode and cathode were immersed in a 0.1-molar solution of tetraethylammonium-tetrafluoroborate in acetonitrile. The resulting battery was charged with a 3.5-volt dry cell. The charged battery exhibited an open- circuit voltage of 3.3 volts. The cell was then discharged at short circuit and subsequently recharged. The battery was charged and discharged in this way several times yielding an open-circuit voltage of 3.3 volts each time. The coulomb efficiency of the charge/discharge process was 30%. Within experimental error, the battery was repeatedly recharged to 40% of its initial capacity.

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