KR900003149B1 - Battery electrodes fabricated with polymers - Google Patents

Abstract

Battery electrodes are fabricated with polymer and a current collector. Thus, e.g. join Pt/poly-2,2'-(para-phenylene)- 6,6'bibenzoxazole/Et4NBF4, acetonitrile/poly-2,2'-(para-phenylene)-6, 6'-bibenzoxazole/Pt cell with doped Pt wires (with bibenzoxazole in 5% methanesulfonic acid and subsequent neutralizing in Et3N/ EtOH) by immersing in 0.1M Et4NBF4/acetonitrile to give battery: when charging with a 3.5V dry battery, then charged-battery shows 3.3V of open- circuit voltage.

Description

Cells bound by electroactive polymers

1 is a detailed view of a cell incorporating an electroactive polymer electrode.

The present invention relates to a battery. In particular, the present invention relates to a battery comprising a polymer which is easy to handle, stable and conductive as an electrode. Extensive research has been carried out on stable, lightweight, high energy density and rechargeable rechargeable battery systems. Among the many other batteries, two important applications for such secondary cells are the storage of electrical energy for electric vehicle propulsion and the electrical application of cargo load measurement.

Current battery technologies under active research have experienced various drawbacks. Many new lightweight secondary batteries under investigation use materials that are naturally combustible or highly toxic, such as molten lithium, sodium and sulfur. Other systems, such as metal air cells, use molten carbonate electrolytes that require carbon dioxide to draw off effluent gas to the air electrode to avoid acid buildup. Perhaps many other useful cell electrode materials are harmed by the dendritic crystalline form by electrolytic precipitation. Therefore, it is not suitable for repeated charging and discharging. These factors are the result of a series of studies on selective cell technology.

Recently, a new approach has been introduced for secondary cells incorporating electrically conductive polymer polyacetylene. The polyacetylene polymers were introduced in US Pat. Nos. 4,222,903 and 4,204,216, both of which are incorporated herein by reference. Polyacetylene is an example of an organic polymer that can be made conductive by a suitable dope process. A polymer that is conductive during electrochemical doping may be used as an electrode in a battery. The ability to repeatedly charge and discharge such polymers is provided for use as electrodes in secondary batteries.

The manner in which charging is done to polyacetylene is generally an optional technique of interest for making batteries as it does not involve electrical deposition and requires no hazardous materials.

Nevertheless, polyacetylene materials experience many drawbacks. Polyacetylene, as its filled form, is not chemically safe and severely limits the lifetime of some secondary battery devices incorporated into this polymer.

In addition, the material cannot be made into a form that is easy to handle. Easy-to-handle organic polymers are defined as polymers that can easily be shaped and shaped and molded and pressed into the required material from the end of the polymerization reaction of the organic polymer or from a liquid state, that is, from a molten and cloudy fluid state or from a solution.

Another electrically conductive polymer such as poly-para-phenylene, polyethylene, vinylene and the like will experience the same defects as polyacetylene. Lack of ease of handling limits cell arrangement and chemical instability severely limits the electrode stability of the cells to which it is bonded. Strictly limit the cell's electrochemical safety. The electrochemical safety of a cell is related to its ability to maintain the required charge level by prolonging shelf life (save life) and then by repeated charge-discharge cycles (circulation life).

Thus, it would be desirable to have a stable, lightweight, primary or secondary battery that includes electrodes of easy-to-handle, electroactive polymers that can be combined into the required electrode form from solution or from a melt. Its electrode must be electrochemically charged to produce a lightweight, high energy density primary cell anode or cathode, and a conductive electrode material capable of producing it, and conversely, to produce a secondary cell. do.

Further, it is more desirable to have a substance or substances that can be widely substituted as a side chain atomic substituent in an atom, atomic group, or polymer backbone, which affects the electrical and morphological mechanical properties of the electrode, which is a polymer of a battery. It is necessary. Furthermore, in order to have electrical stability, it is also necessary for the repeating monomers of the corresponding monomers to have an electrode bonded with a polymer of cyclic repeating repeating monomers which can form stable cations or anions by reversible electrochemical redox. Would be desirable.

It is also desirable to have a stable, lightweight battery that can be modulated by polymer-process technology and optimized for use, which is a well-known technique that has been mastered by anyone in the solution process or melting process technology of traditional polymeric materials. In addition, it would be desirable to have a cell that can be operated under conventional closed conditions and that does not contain any high toxicity or naturally combustible materials.

Higher power densities and energy densities than traditional cells are also desirable. Moreover, in order to increase the electrode surface area and thereby increase the power density, a lightweight primary or two comprising a plurality of thin polymer electrodes sandwiched together in a thin layer that can be combined into a free form electrode which is not limited by various rules. It will be necessary to have a secondary battery. In electric vehicle applications, these free forms can occupy only a small amount of space in the vehicle, such as panels inside the doors, trunks, hoods, under or inside the seats.

I invented a primary or secondary cell that combines at least one electroactive organic polymer electrode with desirable properties as described above. In the simplest form of an electrode, an electrode that can be coupled to a cell is either a current collector, such as a metal wire or a metal foil, or any other electrical conductor, connected to the current collector, or a straight-line, easy-to-handle electrical collector that surrounds the current collector. Active polymers. The linear polymer can undergo reversible oxidation or reversible reduction in a state of charged conductivity. The polymer exhibits great stability with its conductivity filled as an electroactive polymer. An electroactive polymer is defined as a polymer that has a conductivity that is modified to a greater conductivity than the pure or unmodified state of the polymer as an electron acceptor or electron supply semifluid.

Linear polymers are heterocyclic ring systems containing at least one group 5B or 6B atom (IUPAC) in which none of the ring carbon atoms are saturated, and at least one group 5B or 6B in which none of the ring carbon atoms are saturated and not as a bonding unit. A heterocyclic ring system including a group atom and a repeating unit of the double group in the form of a monomeric repeating unit capable of forming a stable ionic substance, capable of undergoing reverse oxidation, reduction or both, and the bonding unit being heterocyclic It includes repeating units of a double group selected from an atomic group consisting of a conjugated system or a mixture of atoms or groups of atoms that maintains the orbits in duplicate with the ring system.

The repeating unit of a double group is defined as the basis of the smallest structure of the polymer backbone having two inadequate linkable positions. These are used to stretch the polymer backbone. The repeating unit of the double group is selected from an atomic group consisting of a heterocyclic ring system, a heterocyclic ring system, a bonding unit or a mixture thereof. The heterocyclic ring system contains at least one Group 5B or 6B atom (IUPAC system). In a heterocyclic ring system, none of the ring carbon atoms are saturated. In particular, heteroatoms are selected from the group consisting of nitrogen, phosphorus, arsenic, antimony and bismuth for group 5B atoms, corals for group 6B atoms, sulfur, selenium and tellurium. Nitrogen, oxygen and sulfur are preferred heteroatoms.

Since heteroatoms are separated between ring systems, the heteroatoms do not occupy the ring fusion position when the ring system consists of fused rings. Furthermore, when more than one ring atom is selected as a single or fused heterocyclic system, when there are less than two adjacent nitrogens, none of the two heteroatoms can be adjacent unless both of them are nitrogen.

The monomeric repeating unit is defined as a repeating unit of a double group in which the insufficient position is substituted with a hydrogen atom. The monomeric repeating unit is a stable ionic material and must be able to undergo reversible oxidation or reversible reduction. Stable ionic materials are defined as concentrated charged atomic or molecular substances that maintain their chemical nature through important chemical processes.

Coupling units are defined as any atom or group of atoms capable of bonding a heterocyclic ring system with any polymer chain without adversely affecting the reversible oxidation or reversible reduction of the polymer. The binding unit must be conjugated or maintained with a pi orbit that overlaps with the heterocyclic ring system.

Pure polymers that are easy to handle can be treated with reversible electrochemical reduction to give them electrical activity. This is accomplished by immersing the pure polymer in a suitable electrolyte solution and using the polymer as an electrode of an electrochemical cell. It is preferable that the electrolyte solution expands the polymerized product. Passing a current through such a cell results in the polymer being partially or fully reduced or oxidized (depending on the direction of current flow) and the charge-reinforced cation or anionic semifluid from the used electrolyte binds into the polymer. The result is an electroactive polymer consisting of a main chain of filled polymer which is conductive and combines a packed reinforced ionic semifluid. The charge of the polymer and the charge reinforced ionic semifluid are balanced so that the electroactive polymer is electrically neutral. Moreover, electrochemical oxidation or reduction proceeds only by electron transfer. The charge reinforced anions or cations are associated with the charged polymer backbone but do not chemically react with or modify the backbone.

Electrochemical polymers have greater conductivity than that of pure polymers. Preferably there are several types of material whose conductivity is greater than that of pure polymers.

The process by which the polymer becomes electroactive can also be used for storage when the polymer is used as an electrode of a primary electric or secondary battery. Filling is condensed in the same process as described above where the pure polymer undergoes both oxidation and reduction to form a charged polymer backbone that is filled with an anionic or cationic semifluid that is replenished. In this way, the polymer of the present invention can form either electrode.

If the positive electrode material is selected to have more negatively charged redox transitions than polymers such as lithium, sodium and the like, the polymer is the negative electrode.

If the negative electrode material is chosen to have a redox transition with less negative charge than polymers such as copper, polypyrrole and the like, the polymer is the positive electrode. The voltage of the cell is determined as the redox transition difference of each electrode of the electrode material. Therefore, it is recommended that the anode has a reduction potential with a negative charge and the cathode has a oxidation transition with a positive charge.

Known as polymer n-type polymers that can be reversibly reduced. They are particularly suitable for use as positive electrodes. The n-type electroactive organic polymer of the present invention is obtained by binding a cation which charge neutralizes by electrochemically reducing the pure polymer into a number of anions. Reversible oxidizable polymers are known as p-type polymers. They are particularly suitable for use as negative electrodes. P-type electroactive organic polymers are obtained by electrochemically oxidizing a pure polymer with many cations and binding cations that charge neutralize therein.

As electrodes the polymer is stable in the electrically active or charged state of the material. This is because these materials are composed of monomeric repeating units composed of repeating units having double groups which form stable cations and anions by electrochemical oxidation or reduction. This gives the electrical stability of the cells combined with them.

The energy density of a cell in which these polymers are bonded as one or both electrodes can be calculated from the molecular weight of the polymer and the redox transition of the electrochemically active repeating unit. This cell exhibits a greater energy density of at least 50 w-hrs / kg and preferably greater than 10 w-hrs / kg may be combined with the polymers described above. The electrodes can be joined while maintaining intimate space as a thin film because the polymers maintain stability of their structure and dimensions during the charge and discharge cycles. In contrast, conventional inorganic electrodes require a strong resistance electrode support to provide surface area for the liquefaction and redeposition of active electrode metals, and short circuits in cells that cause nonuniform increases in metal electrode materials or increased dendritic stones. It requires a larger space between the electrodes to avoid the circuit.

Since the present polymer electrode only needs sufficient electrolyte solution to sufficiently expand the polymer, the diffusion of the ionic semi-fluid charged and reinforced in and out of the polymer molding is quite sufficient to maintain a proper discharge rate. The electrolyte ions may be present primarily in the solid state as a slurry in the minimum optimal saturated electrolyte solution between the two electrodes. The nature of these electrolyte ions makes it possible to achieve energy density values that in many cases exceed those of conventional cell technologies.

The fact that strong resistive electrode supports and large internal electrode spaces are not required for these polymer cell electrodes is also that the surface area of the electrodes can be increased in effect without significant increase in the total weight of the cell. This can be accomplished by assembling the cell into a series of thin plate electrodes sandwiched together in thin layers. A cell coupled with a plurality of thin plate electrodes formed of multiple layers has an extremely high surface area in volume ratio and can substantially achieve a higher power density than is possible with conventional battery electrode materials. Combined with any required electrode size with the ability to mold and shape easy-to-handle polymers, this part allows the formation of battery models in very free and useful forms. For example, such batteries do not need to be enlarged and are used to power electric vehicles with right-angled trunk space, but they can also be shaped to fit the body of the car.

Easily handled, electrically active unsaturated heterocyclic system polymers can bind ionic electroconductive variants, and polymers capable of undergoing electrochemical modifications of the polymers are described in a US patent application filed on November 27, 1982. No. 442,531, which is hereby incorporated by reference in its entirety. Such polymers are useful as electrode materials in the cells of the present invention. Preferred units of the double group forming the main chain of the linear polymer include the following materials.

Suitable fused 6,6,6-membered ring system polymers include thianthrene, phenoxadrin, phenoxazine, N-alkylphenothiazinedihydro-pazine, dialkyldihydrophenazine, dibenzodioxazine and double groups thereof. Substituted derivatives of materials and mixtures thereof. The double group is connected to the outer carbocycle ring or to the carbocycle ring in the central ring via nitrogen. Preferably, the double group is pointed with a bonding unit such as phenylene, vinylene, dithiophenylene and 2,5- (1,3,4-oxadiazoldiyl). More specific are poly-2,5-phenoxazine, poly-2,5- (3,7-dimethyl) -phenoxazine, poly-2,5- (1,4-phenylene) phenoxazine, poly-3, 7- (N-methylphenothiazine-2,5- (1,3,4-oxadiazole), poly-3,7- (phenoxazine-4,4'-dithiobiphenylene), and poly- Polymers such as (1,4-dithiophenylene-2,6-thiaanthrene).

These polymers are p-type polymers capable of undergoing reversible oxidation and are good materials for use as the negative electrode of the present invention. See, for example, US Patent Application Nos. 442,400 and 442,393, filed November 17, 1982, which are incorporated herein by reference in their entirety.

Suitable fused 5,6-membered ring system polymers are joined by double groups of benzoxazoles, benzothiazoles, benzoselenazoles, N-alkyl-substituted benzimidazoles, substituted derivatives thereof and the like. Specific examples are poly-2,2 '-(p-phenylene) -1,1'-dimenyl-5,5'-bibenzimidazole, poly-2,2'-(p-phenylene) -5 , 5-bibenzoxazole, and poly-2,2 '-(p-phenylene) -5,5'-bibenzthiazole.

The polymer can be subjected to reversible reduction to form a stable N-type polymer. These polymers are preferably used as the cathode material of the present invention. Particularly good polymers are poly-2,2 '-(p-phenylene-6,6'-bibenzoxazole, poly-2,2'-(p-phenylene) -1,1'-dimenyl-6 , 6'-bibenzimidazole, and poly-2,2 '-(p-phenylene) -6,6'-bibenzthiazole These polymers are N-types that can undergo reversible oxidation and reduction And p-type characteristics.

These polymers are particularly preferably used as the negative electrode material (ie when the polymer is n-type) or the positive electrode material (ie when the polymer is p-type) of the present invention. Another preferred polymer is poly-2,2 '-(m-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(m-phenylene) -1,1'-dimethyl -6,6'-bibenzimidazole, poly-2,2 '-(m-phenylene) -6,6'-(bibenz-thiazole, and poly-2,2 '-(N-methyl- p, p'-aminodiphenylene) -6,6'-bibenzoxazole These polymers can undergo reversible oxidation to form stable p-type polymers. Preference is given to US Patent Application No. 442,392, filed on November 17, 1982 and incorporated herein by reference in its entirety.

Suitable 5,6,5-membered ring system polymers include 1,7-dimethyl-benzo [1,2-d: 4,5'd '] diimidazole: benzo [1,2-d: 5,4-d '] Bisthiazole; Benzo [1,2-d: 5,4-d '] bisthiazole; Benzo [1,2-d: 4,5-d '] bisselanosol; Benzo [1,2-d: 4,5-d '] bisselenazole; Benzo [1,2-d: 4,5-d '] bisterrazole; 1,7-dialkylbenzo [1,2-d: 4,5'd '] imidazole and 1,8-dimethylbenzo [1,2-d: 3, such as selenazolo 5,4-f benzothiazole 4-d '] diimidazole; Benzo [1,2-d: 5,4-d '] bioxazole: benzo [1,2-d: 4,5-d'] bioxazole; Benzo [1,2-d: 3,4-d '] bisoxazole; Benzo [1,2-d: 3,4-d '] bisthiazole; Such as 1,3-dialkyl-benzo [1,2-d: 3,4-d '] diimidazole and substituted derivatives thereof and double groups of mixtures thereof. For example, poly-2,6- (p-phenylene) -benzo [1,2-d: 5,4-d '] bis-oxazole, poly-2,6- (p-phenylene) -1 , 7-dimethyl-benzo [1,2-d: 4,5-d '] diimidazole, poly-2,6- (p-phenylene) -benzo [1,2-d: 4,5-d Preference is given to '] bisthiazole and poly-2,6- (p-phenylene) benzo [1,2-d: 4,5-d'] bisthiazole. Preferred polymers exhibit n-type properties. See, for example, US Patent Application No. 442,394, filed November 17, 1982 and incorporated herein.

Suitable monocyclic heterocyclic ring system polymers include triazoles such as thiadiazoles, oxadiazoles and the like, heteroazoles and oxazoles and thiazoles; It is composed of cyclic double groups of heteroazoles such as all of the above monocyclic heterocyclic systems which bind 1,4-phenylene as a binding unit. Optionally these systems can be combined with other preferred binding units. Suitable polymers include poly-1,4-phenylene-2,5- (1,3,4, -oxadiazole), copolymers of oxadiazole and thiadiazole poly-1,4-phenylene-2 , 5- (1,3,4, -thiadiazole), poly-4,4'-N-methylaminodi-phenylene-2,5- (1,3,4, -oxadiazole), poly -1,4-phenylene-2,4- (1,3-diazole), poly-1,4-phenylene-2,5- (1-phenyl-1,3,4-thiazole), and Poly-1,4-phenylene-2,5- (1,4-dithiene).

Preferred polymers exhibit n-type properties.

These polymers are preferably used as the positive electrode material of the present invention. Examples are shown in US Patent Application Nos. 442,396, 442,397, 442,398 and 442,399, both filed November 17, 1982 and hereby incorporated by reference. Only those compounds in which the corresponding monomeric repeating unit as a monocycle type system can undergo reversible reduction or reversible oxidation with a stable ionizing material fall within the scope of the claims.

Of course, some of the mono or conjugated heterocyclic systems may be substituted with one or more substituents as long as the ring carbon atoms remain unsaturated.

Suitable polymers, for example, consist of units of cyclic double groups in a 6,6-membered nitrogen-containing heterocyclic ring system. The fused reduced nitrogen atoms up to 1-6 and preferably 1-4 nitrogen atoms. The nitrogen atom is separated between two or less consecutively bonded nitrogens in the ring and the fused ring without the nitrogen occupying the ring fusion site. These polymers exhibit n-type characteristics and are preferably used as the cathode material of the present invention. Suitable polymers are introduced in US Patent Application No. 264,915, filed May 18, 1981, and Application No. 370,231, filed April 22, 1982, filed September 21, 1981. All descriptions and disclosures in this application are complete and are incorporated herein by reference for all purposes.

Suitable examples of single nitrogen fusion-ring systems are several of the dual groups of quinoline and isoquinoline. Preferred quinoline polymers exhibit n-type electrical conductivity.

Suitable examples of two nitrogen condensed ring systems are ninoline, quinazoline, quinoxaline, 2-phenylquinoxaline, phthalazine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthy Lidine, 1,8-naphthyridine, 2,6-naphthyridine, and several of the dual groups of copyrins and similar substances. Suitable examples of three nitrogen ring systems include 1,2,4-benzotriazine; Pyrido [3,2-d] pyrimidines; Pyrido [4,3-d] pyrimidines; Pyrido [3,4-d] pyrimidine; Pyrido [2,3-d] pyrimidine; Pyrido [2,3b] pyrazine; Pyrido [3,4-b] pyrazine; Pyrido [2,3-d] pyridazines; Pyrido [3,4-d] are some of the double groups of pyridazine and similar materials. Suitable examples of four nitrogen fused ring systems are described above with some of the double groups of [4,5-e] -as-triazine, pyrimido [5,4-d] -as-triazine and similar materials. All fused nitrogen-ring systems are known and introduced from RingIndex 2nd Edition and Splitter I, II, and III Peterson et al., American Chemical Society. These polymers are preferably used as the positive electrode material of the present invention. The molecules can be prepared by known methods such as the treatment of zinc chloride (zncl ₂ ) or iron chloride (Fecl ₃ ) with alkyl iodides or by suitable duplexes such as disodium sulfide, disodium salts of ethylene glycogen and the like. It polymerizes into a polymer by the dichlorination reaction made by reacting with a substitution molecule.

Double groups can modify substituents, such as the supply or removal of electrons, by known methods of modifying polymer properties.

인데 여기에서 Ar은 페닐렌이나 비페닐렌이고 R₂는 저급알킬, C₁-C₄예컨대 디페닐, 메틸아민이다.The double groups can also be converted into one or more binding units. Preferred binding units are phenylene, biphenylene, vinylene and

Wherein Ar is phenylene or biphenylene and R ₂ is lower alkyl, C ₁ -C ₄ such as diphenyl, methylamine.

Suitable polymers in which the intermediate nitrogen is in ionized form include N-alkyl quinolinium and similar materials for the compound.

The electroactive polymer of the present invention has the following general formula.

-[R (X) _a- (R ') _c- (Y) _b- ] _n ^{(± Sd)} [M ^{± S} ] _d

Where a is 0 or 1, b is 0 or 1, c is 0 or 1, n is an integer between 1 and 20,000, d is an integer between 1 and 40,000, and S is an integer of 1,2 or 3 R is a ring system of an unsaturated or saturated heterocyclic double group, R 'is a ring system of the same double group in R or a ring system of a different double group, x is a bonding unit consisting of a single atom or a group of atoms and y is from x A binding unit that is the same as or different from the binding unit, and m is a repeating unit in which electrical charge is circulated

An atom or group of atoms that acts like a charge-filling ion, as opposed to the charge represented by

Repeating units form the polyanions or polycations of the electrochemical polymer. The R atom group, which is a double group, is a substituted or unsubstituted heterocyclic system described above. For example, quinoline, isoquinoline, substituted derivatives or mixtures thereof are preferred. Better quinoline polymers are those having double groups linked to the 2,6 and 3,6 positions. Substitution at the 4-position is preferably the same as poly-2,6- (4-phenylquinoline). Another preferred polymer consists of quinoxaline unit substituted quinoxaline or mixtures thereof. Alternatively, the double groups can separate the double groups into one or more bond units of x or y, which are atoms or groups of atoms capable of bonding with the polymer chain. Another binding unit, x and y

It may be selected from the atomic group consisting of.

Wherein R ₁ is lower alkyl, C ₁ -C ₆ aryl and cycloalkyl, R ^V , R ^VI and R ^VII are hydrogen or methyl, methoxy, halogen and mixtures thereof and R ₂ is lower alkyl C ₁ -C ₄ is parasubstituted phenyl and Ar is phenylene or biphenylene.

Another suitable binding unit is the same as the application introduced above and described above. It is preferable that the bonding unit is selected from

이다.

to be.

The following structural formulas represent preferred electroactive n-type polymers that are substituted and / or bound to the binding units. These are preferably used as the cathode material of the present invention. Suitable polymers have the following structural formula:

Another suitable polymer has the structure

Another suitable polymer has the structure

Another preferred polymer has the structure

Where Z is a binding unit. Another preferred polymer is obtained when R and R 'are quinoline double groups with substituent atom groups R ^II at the 4 position and R ^VII is methyl or hydrogen and the polymer has the structure

Yet another suitable polymer is wherein R ^III is phenyl and R ^VII is hydrogen. Preferred polymers of poly (phenyl quinoxaline) have the structure

The cell will become more apparent when described in conjunction with the first column. 1 shows a primary or secondary battery. The cell 10 has a case 12 including a positive electrode 14 and a negative electrode 16 separated by a separator 18. The battery is charged by reducing the positive electrode and oxidizing the negative electrode when the electrodes 14 and 16 are immersed in the auxiliary electrolyte dissolved as a solvent. The auxiliary electrolyte results in a salt or other cation-anion pair dissolved in a suitable solvent. The auxiliary electrolyte and the solvent result in the electrolyte 20. The wires 24 and 22 are connected to the positive electrode 14 and the negative electrode 16, respectively, to charge and discharge the battery 10. When the electrodes 14 and 16 are bonded to the polymer, the electrodes 14 and 16, like the platinum wire or the thin plate, are bonded onto the current collector or in contact with the current collector (not shown in the drawing) or inverse to the polymer. It is combined with other suitable low resistance conductive materials that do not react. Also suitable are materials such as carbon felt, graphite, glassy carbon, platinum, gold, nickel and the like. Better yet, the current collector has a conductivity of about 100 ohm ^-1 cm ^-1 or more.

Heterocyclic ring system polymers may be used as the anode 14 or the cathode 16. Even better is that the n-type polymer is used as the positive electrode and the p-type polymer is used as the negative electrode. Polymers such as the above two substances, for example, wherein the anode 14 is a polymer such as poly-2,6-quinoline or poly-2,6- (4-phenyl) quinoline, and n-type electroconductive polymers as their electroactive forms. Poly-2,5- (phenoxazine, poly-3,7- (N-methylphenothiazine) 2,5- (1,3,4-oxadiazole), poly-2,2- (methphenylene Composed of polymers such as) -6,6'-bibenzoxazole and the like, all of these p-type polymers as electrochemical forms include a negative electrode 16. Optionally, the cell of the present invention is a positive electrode. Alkali metals such as lithium, sodium and the like and p-type heterocyclic polymers as cathodes may be included.Other materials whose redox transitions are much more negative than the redox transitions of selected p-type polymers acting as cathodes It can also act as an anode, thus also belonging to the claims of the present invention.

Another preferred representation of the present invention involves the use of n-type heterocyclic polymers as the positive electrode and materials that are more positively charged than the redox transitions of the n-type heterocyclic polymers in which redox transitions can act as negative electrodes. Thus, materials such as gold and iron or other polymer materials such as polyacetylene or polypyrrole may be used as the negative electrode.

Yet another preferred example of the present invention focuses on the use of an n-type heterocycle polymer as a cathode and a material that is more negatively charged than the redox transition of the n-type heterocycle polymer, where the redox transition can act as an anode. do. Therefore poly-2,6- (4-phenyl) quinoline or poly-2,6- (4-phenyl-N-methyl-quinolinium may be the negative electrode and alkali metals such as lithium and sodium and the like may be the positive electrode Can be.

N- such as anode 14 is poly-2,6-quinoline, poly-2,6- (4-phenylquinoline), polyquinoxaline substituted derivatives thereof and the like listed in US Patent Application No. 370,231 When preferably combined with the type polymer, the anode is charged by chemically reducing the polyquinoline in the presence of a co-electrolyte cation dissolved in a solvent, i.e. by negative electrical charging. The cation binds to the filled polymer. Similarly poly-2,5-phenoxazine, poly-3,7- (N-methylphenothiazine) -2,5- (1, having negative electrode 16 listed in US patent applications 442,400, 442,393 and 442,392 When combined with p-type polymers such as 3,4-oxadiazole), poly-2,2 '-(m-phenylene) -6,6'-bibenzoxazole, substituted derivatives thereof and the like The negative electrode is electrochemically oxidized in the presence of an auxiliary electrolyte anion dissolved in a solvent, i.e., charged by negative electrical charging. The anion binds to the filled polymer.

Suitable electrolyte cations include Li ⁺ , Na ⁺ , K ⁺ , Ca ⁺ , Mg ⁺ , (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , (C as described in US Patent Application No. 304,410). ₂ H ₇ ) ₄ N ⁺ , (C ₄ H ₉ ) ₄ N ⁺ and similar cations.

The cation may be any cation and salt that can be dissolved in a solvent and does not reversibly react with the electrode material. Suitable electrolyte anion is ^{F -, Cl -, Br -} , ClO 4 -, BF 4 -, NO 3 -, PF 6 -, AsF 6 -, and may be similar to this. Mixtures of salts may be used.

For example, a battery containing a polyquinoline (PPQ) positive electrode with a cationic portion of an electrolyte such as tetrabutyl ammonium tetrafluoroborate dissolved in a solvent such as an acetonitrile solution and [(nBu) ₄ N ⁺ ] was prepared by the following reaction example. It is described as.

^{_{PPQ + (nBu) 4 N +}} ( ^{solution) + e - → PPQ - (} nBu) 4 N +

The anode reaction during discharge of the cell is explained as follows.

_{^{PPQ - (nBu) 4 N +}} → PPQ + (nBu) 4 N + ( solution) + e ^-

In this example, negative electrode 16 may be some material that does not reversibly react with the positive electrode while oxidizing during charging of the cell. Suitable examples of the negative electrode material are silver fluoride, silver chloride, silver coated with silver halides such as silver oxide, polymers such as polyacetylene, polypyrrole, polyphenylenesulfide, polyphenylene or poly-1,6-heptadiene, and other paratype complexes. Intercalated compounds having a redox transition that exhibits a greater positive charge than the redox transition of the cyclic polymer or anode. An insertion electrode is defined as an electrode material having an intimate structure, [Z], which precipitates through electrochemical reaction via an insertion mechanism to produce an insertion compound as follows.

Lix Tix ₂ is an example of a suitable intercalation electrode material. Lix Tix ₂ has a known redox transition of about -0.8 volts.

Addition of the intercalation compound includes chakogenides of group IV-B such as Tis ₂ , TiSe ₂ , group VB metals such as V ₂ S ₅ , V ₂ Se _4.5 , (NH ₄ ) ₃ VS ₄ , (NH ₄ ) _2, a group VI-B metal, and Fes, FeS _2, Cos, CoS _2, Nis, group VIII metals such as Nis ₂ and similar groups such as MoSe _2.

The cathode is a salt form of the polymer or poly -2,6- (N- alkyl lower mold of the polymer, such as 4-methyl -N- key fun of titanium with a suitable anionic ion is ^{Cl -., Br -, F} -, I - _{^{, BF 4 -, ClO 4 -}} , PF 6 -, AsF 6 -, and to the like.

NO _3-

As a better example, see JC S Chem, Com. It may be a pp _y polypyrrole material, as known in the 1979 edition page 635-636. Even better is the negative electrode of some of the p-type heterocyclic polymers described above. If the negative electrode is polypyrrole (pp _y ) contained in a tetrabutyl ammonium-tetrafluoroborate solution dissolved in an acetonitrile solvent, the charging of pp _y in the cell is explained as follows.

pp _y -BF ₄ ^{- _{(solution) → ppy y + BF 4 -}} + e -

All charge and discharge reactions of the secondary battery are described as follows.

With respect to the cell description above, separator 18 is only needed to prevent electrical shorts between the positive and negative electrodes. One suitable example is a fine membrane nylon lattice. Several separators can be used in the present invention as long as they are electrical insulators and do not dissolve in the electrolyte solution and prevent free flow of ions. Another example is the Teflon grating.

Alternatively, if it is chosen that the secondary electrolyte or reverse electrode does not chemically react with the polymer electrode, the separator should be an ion selective membrane. Ion selective separation divides cell 10 into a cation compartment and an anion compartment. For example, ion selective separators are needed when the anode is PPQ and the cathode is silver, iron, copper, zinc, nickel, palladium, tin or other metals that can be made into a bipolar plate.

The solvent portion of electrolyte 20 includes several liquids that dissolve the auxiliary electrolyte in its ionized form. Suitable solvents are electrodes or cases such as acetonitrile, propylene carbonate, tetrahydrofuran, propionnitrile, butylionnitrile, phenyl acetonitrile, dimethylformamide, dimethoxyethane, dimethylsulfoxide, pyridine or mixtures thereof and the like. Are some substances that do not dissolve the separator. Several gelling agents of the known technique suitable for increasing the viscosity of the auxiliary electrolyte without inhibiting the decomposition of the auxiliary electrolyte and the migration of ions therein are suitable, such as starch guar gum and the like. The discharge voltage of the battery is determined by the difference between the redox potential of the positive electrode material and the redox potential of the negative electrode material.

For example, poly-2,6- (4-phenylquinoline) is reduced to a standard calomel electrode (SCE) at a potential of about -2 volts vs. a redox potential of about -2.0 volts. Polypyrrole oxidizes at a potential of about 0 Volts vs, SCE. If a single cell cell is assembled using these two polymers as the positive and negative electrodes, respectively, the nylon mesh lattice separator and the electrolyte solution of tetraethylammonium tetrafluoro borate between the electrodes are dissolved in acetonitrile and consequently release of the cell. The voltage is about 2 volts. This is compared with the voltage of a single cell lead / oxide battery. The six cells in series are supplied in a standard 12 volt system such as an automobile or the like. A slightly larger number of cells can be connected in parallel to obtain the necessary and necessary emission currents.

In an optional example of the invention, the polymer is paired as an electrode material having a more negative redox potential. In this type of cell the polymer functions as a negative electrode. Suitable materials with a more negative electric redox potential that function as the anode are metals such as lithium, sodium, potassium, rubidium, cesium or alloys thereof. The anode is also Li _x WO ₂ . It may be an intercalation compound having more negative electrochemical redox potential than the polymer negative electrode, such as Li _x WO ₂ having a redox potential of about -2.5 volts. For example, a battery may be combined with a PPQ negative electrode and a lithium positive electrode. During discharge of the cell, the PPQ cathode is reduced to negative electrical charge and is doped with a cationic portion of an electrolyte salt containing lithium, such as lithium, perchlorate, dissolved in propylene carbonate. Lithium anodes are electrochemically oxidized. The negative electrode can be electrochemically reduced, i.e. covered with an anionic portion of a lithium containing electrolyte such as lithium perchlorate, which is positively charged and dissolved in propylene carbonate. The cathodic reaction during discharge is illustrated as follows.

PPQ ⁺ e ^- + Li + (solution) → PPQ ^- Li ⁺

The anodic reaction is illustrated as follows.

Li → Li ⁺ (solution) + e ^-

All reactions are illustrated as follows.

The use of the heterocyclic polymers described above in the assembly of the positive and / or negative electrodes represents a significant improvement in the electrochemical stability of cells made up of polyacetylene and other conductive polymeric materials reported to date.

A striking part of the polymers of the present invention provided for this improvement is the fact that these polymers consist of a double group of complex units, with the corresponding monomeric repeat units forming stable cations or anions, respectively, by electrochemical reversible oxidation and reduction. do.

As a result of their electrochemical stability, their batteries may be subjected to repeated severe discharges.

Moreover, the battery exhibits extremely high discharge, corresponding to a peak power density of about 12 kw / 1b. In addition, the depth of discharge and charge is almost 100%.

At 60 cycles of deep charging and discharging, the battery showed no significant change in its characteristics. The battery is not limited to the structure shown.

A cathode, such as the separator poly-2,2'-9m-phenylene) -bibenzoxazole, which combines the replacement layer of the polyquinoline anode and the electrolyte, is wound in a spiral arrangement as shown in the cross-sectional view and is tubular cylindrical in length. Can be assembled. A slightly larger number of alternating layers of anode and cathode material separated by the separator are used to increase the charge storage capacity and power dissipation of the cell.

In describing the electrolyte, the battery, and a method of assembling the battery, the present invention will be described in detail in the following examples. It is not intended, however, to limit the claims of this patent. Obvious modifications by one of the common known art are deemed to be within the claims of the present invention.

Example 1

Platinum / Poly-2,6- (4-phenylquinoline) / tetra butylammonium-bromide, acetonitrile / silver bromide / silver cells combine so that poly-2,6- (4-phenylquinoline) acts as a positive electrode Silver bromide acted as the negative electrode material.

A 10 cm long silver wire was polarized in an acetonitrile solution of Bu ₄ NBr by passing a charge of about 20 kurom to form a silver bromide layer. Platinum wire was immersed in a 5% meta-cresol / phosphorus pentoxide solution of poly-2,6- (4-phenylquinoline) to coat a thin film of poly-2,6- (4-phenylquinoline) and ethanol / triethylamine Neutralized at.

The resulting film was several microns thick. The two electrodes were immersed in a 1 mol solution of acetonitrile of Bu ₄ NBr to keep them in contact with each other. The cell was connected to an electrode and charged with a 2.7 volt battery for several minutes. As a result, the battery had an (開circuit voltage and short circuit current of 340 microamps of 0.75 volts open circuit corresponding to a current density of 3.5 ms Amp / cm ^2.

Example 2

Combine platinum / poly-2,6- (4-phenylquinoline) / tetraethylammonium-tetrafluorobotate and acetonitrile / polypyrrole / platinum cells to convert poly-2,6- (4-phenylquinoline) as a cathode Polypyrrole was used as the negative electrode material. AF Diaz, JCS Chem. com. 1979 edition, was electroplated (電着) a platinum foil electrode in 10Cm area ² in accordance with the process disclosed in pages 635-635. A film of poly-2,6- (4-phenylquinoline) was electrodeposited on the second platinum epoch in the same manner as described in Example 1 above. These two electrodes were immersed in a 0.5 molar solution of acetonitrile of tetraethylammonium-tetragluoroborate. The electrodes were separated by nylon mesh. The cell was charged with a 2.7 volt battery over several minutes. As a result, the battery exhibited an open circuit voltage of 21 volts and a short circuit current of 250 milliamps, corresponding to a current density of about 12 milliamps Amp / Cm ² . The discharged battery was recharged over several minutes by connecting an external 2.7 volt battery. More than 100 charge-discharge cycles were carried out in this manner with no change in open-circuit voltage, short-circuit current or battery capacity.

Example 3

Combine lithium / lithium perglolate, propylene carbonate / poly-2,6- (4-phenylquinoline) / platinum battery to make poly-2,6- (4-phenylquinoline) as a negative electrode material and lithium as a positive electrode It was made into a substance. While the lithium anode with a propylene carbonate solution of LiClO ₄ passes through the charge in the gun -58 kurom pure Li fills platinum 20Cm ² - was prepared by electrodeposition on the electrode sheet. A similar platinum-thin electrode was coated with poly-2,6- (4-phenylquinoline) of the thin film as in Example 1. The cell was immersed in a propylene carbonate solution of LiClO ₄ while the two electrodes were arranged facing each other and separated by a nylon mesh barrier to avoid short circuits. The open circuit voltage of the battery was 2.37 volts as a short circuit current of 95 milliamps corresponding to a current density of 5 milliamps Amp / Cm ² . An external charge-discharge cycle over the discharge cell over about one minute resulted in similar results but with a gradual drop in battery capacity.

Example 4

Poly-2,6- (4-phenyl by combining carbon / poly-2,6- (4-phenylquinoline) / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,5-phenoxazine / carbon cells Quinoline) as the active cathode material and poly-2,5-phenoxazine was used as the active cathode material. Reticulated carbonaceous carbon masses were coated with poly-2,6- (4-phenylquinoline) immersed in a 5% meta-cresol / phosphorus pentoxide solution of this polymer and neutralized in an ethanol / triethylamine bath. A second net-like glassy carbon mass was electrochemically oxidized with a phenoxazine polymer into a THF solution of the polymer, resulting in coating of the electrodeposited poly-2,5-phenoxazine film. The electrode was then rinsed with THF and dried with inert gas. The electrode was then immersed in a 0.1 mole solution of acetonitrile of tetraethylammonium-tetrablueorborate and electrochemically reduced to obtain a carbon electrode such as a neutral glass coated with a thin film of neutral poly-2,5-phenoxazine. Left. The two coated carbon anodes and cathode electrodes were immersed in a 0.5 mole solution of acetonitrile of tetraethylammonium-tetrafluoroborate to separate into thin nylon nets. The battery was charged with a 1.5 volt battery to fully charge and an open circuit voltage of 3.0 volts was obtained. The short-circuit discharge of this cell exhibited a current plateau of about 125 milliamps for most of the discharges, with a nearly complete discharge followed by a sharp drop in current. The battery was then recharged with a battery to obtain the same reaction by 3.0 volt open circuit voltage and short circuit discharge. Repeated charge / discharge cycles showed no change in this short circuit discharge curve, battery capacity, or open circuit voltage. This cell exhibited greater efficiency than 95% coulomb. (I.e. greater than 95 ° of injected charge recovered during discharge.

Example 5

Platinum / poly-2,6- (4-phenylquinoline) / tetraethylammonium-tetrafluoroborate, acetonitrile / poly- [2,6- (N-methyl-4-phenyl) quinolinium] / platinum battery By combining, poly-2,6- (4-phenylquinoline) was used as the active cathode material and poly- [2,6- (N-methyl-4-phenyl) quinolinium] was used as the active cathode material. Two platinum wires were coated with poly-2,6- (4-phenylquinoline) as described in Example 1. One of these wires was treated with dimethylsulfate, cut for 10 minutes, to bond nitrogen, resulting in the coating of platinum with a quinolinium polymer film. Two coated wire positive and negative electrodes were immersed in a solution of 0.1 mole of acetonitrile of tetraethylammonium-tetrafluoroborate. The poly-2,6- (4-phenylquinoline) sheathed wire was connected to three electrode potentiometers with the aid of a platinum pre-electrode with 1.8 volt Vs. Reduced to SCE. The control and preliminary electrodes were removed from the solution, leaving only two coated lines. In this way, the charged battery exhibited an open circuit voltage of 1.0 volt. The cell was then discharged in a short circuit and subsequently recharged at 1.2 volts. The battery was repeatedly charged and discharged in this manner several times to obtain an open circuit voltage of 1.0 volt per hour. The coulomb effect during the charge and discharge process was 80%. Within experimental errors, the cell was repeatedly recharged to 100% of its original capacity.

Example 6

Platinum / poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,5'-phenoxazine / platinum battery And poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole as the active cathode material and poly-2,5-phenoxazine as the active cathode material. The platinum wire was immersed in a 5% methanesulfonic acid solution of the bibenzoxazole polymer, covered with a thin film of this polymer and neutralized in an ethanol / triethylamine bath. A 1 Cm ² platinum leaf was coated with a thin film of poly-2,5-phenoxazine and the tetrahydrofuran of this polymerization was oxidized to electrochemically to obtain an oxidized electrical precipitation film. The electrode was then rinsed in tetrahydrofuran and dried over an inert gas. Next, the electrode was immersed in a 0.1 molar solution of tetraethylammonium-tetrafluoroborate and electrochemically reduced to obtain a platinum thin leaf coated with a neutral poly-2,5-phenoxazine film. Both the wire positive electrode coated with the benzoxazole polymer and the platinum thin leaf cathode coated with the phenoxazine polymer were immersed in a 0.1 mol solution of acetonitrile of tetraethylammonium tetrafluoroborate. The battery thus treated was charged with a 3.5 volt battery. The charged battery exhibited an open circuit voltage of 3.0 volts. The battery was then discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 3.0 volts per hour. The coulomb effect in the charge / discharge step was 80%. Within the error range of the test, the battery was repeatedly recharged to 100% of its original capacity.

Example 7

Platinum / poly-2,6- (p-phenylene) -benzo [1,2-d: 5,4-d] bisoxazole / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,5 -Phenoxazine / Platinum cells were combined, where the benzobisoxazole polymer acted as the active cathode material and the phenoxazine polymer acted as the active anode material. The platinum wire was immersed in a 5% methanesulfonic acid solution of benzobisoxazole polymer to be coated with a thin film of this polymer and neutralized in an ethanol / triethylamine bath. The 1 Cm ² platinum leaf was coated by electrochemically oxidizing a solution of tetrahydrofuran of the polymer using a thin film of poly-2,5-phenoxazine, resulting in an oxidized and electrically precipitated film. The electrode was then rinsed with tetrahydrofuran and dried over an inert gas. The electrode was then precipitated in a 0.1 mole solution of acetonitrile of tetraethylamine tetrafluoroborate and electrochemically reduced to obtain a platinum foil coated with a neutral poly-2,5-phenoxazine film. Both the positive electrode wire coated with the benzobisoxazole polymer and the negative electrode platinum thin film coated with the phenoxazine polymer were immersed in a 0.1 mol solution of acetonitrile of tetraethylammonium-tetrafluoroborate. The battery thus charged was charged with a 3.5 volt battery. This charged cell exhibited an open circuit voltage of 3.1 volts. The cell was then discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 3.1 volts per hour. The cell was repeatedly recharged to within 65% of its original capacity within the laboratory error range.

Example 8

Platinum / poly-2,6- (para-phenylene) -benzo [1,2-d: 4,5-d] thiazole / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,5- In combination with the phenoxazine / platinum cell, the benzobisthiazole polymer acted as the active positive electrode material and the phenoxazine polymer as the active negative electrode material. The platinum wire was immersed in a 5% methanesulfonic acid solution of benzobisthiazole polymer to be coated with a thin film of this polymer and neutralized in an ethanol / triethylamine bath. A 1 Cm ² platinum leaf was coated with a poly-2,5-phenoxazine thin film to electrochemically oxidize the solution of this polymer, and the material thus oxidized to obtain an electrodeposited film. The electrode was then rinsed with tetrahydrofuran and dried over an inert gas. This electrode was then immersed in a 0.1 mole solution of acetonitrile of tetraethylammonium-tetrafluoroborate and electrochemically oxidized to obtain a platinum thin film coated with a neutral polyphenoxazine film. Both the wire positive electrode coated with the benzobisthiazole polymer and the platinum thin leaf negative electrode coated with the phenoxazine polymer were immersed in a 0.1 mol solution of acetonitrile of tetraethylammonium tetrafluoroborate. This battery was charged with a 3.5 volt battery. This charged cell exhibited an open circuit voltage of 3.4 volts. The cell was then discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 3.4 volts per hour. The cells were repeatedly recharged within laboratory errors to 97% of their original capacity.

Example 9

Combine platinum / poly-para-phenylene-2,5- (1,3,4-oxadiazole / tetraethylammonium-tetrafluoroborate acetonitrile / poly-2,5-phenoxazine / pratinium cells Poly-para-phenylene-2,5- (1,3,4-oxadiazole) was used as an active cathode material, and poly-2,5-phenoxazine was used as an active cathode. butylene-2,5 (1,3,4-oxadiazole) by immersing in a 5% sulfuric acid solution was neutralized in the polymer to be coated with a thin film and to an ethanol / triethylamine bath. 1Cm the sheet ² of platinum film bakyeop Coated with a poly-2,5-phenoxazine of, but electrochemically coated with a tetrahydrofuran solution of the polymer to obtain an oxidized and electrodeposited film.Then the electrode was rinsed with tetrahydrofuran After drying with an inert gas, the electrode was dried with 0.1 mol of tetraethylammonium-tetrafluoroborate. It was immersed in the solution and electrochemically reduced to obtain a platinum thin film coated with neutralized polymer-2,5-phenoxazine, both a wire positive electrode coated with this oxadiazole polymer and a platinum thin film negative electrode coated with a phenoxazine polymer. It was immersed in 0.1 mol of acetonitrile solution of tetraethylammonium-tetrafluoroborate The cells thus treated were charged with a 3.5 volt battery, which showed an open circuit voltage of 3.4 volts. The battery was discharged in a circuit and subsequently recharged, and the cell was repeatedly charged and discharged in this manner to obtain an open circuit voltage of 3.4 volts per hour. Was 99%.

Example 10

Platinum / poly-2.6- (para-phenylene) -benzol [1,2-d: 4,5d '] bisthiazole / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,2'-(meta -Phenylene) -6,6'-bibenzoxazole / platinum cells combined, with the benzobisthiazole polymer as the active cathode material and poly-2,2 '-(meth-phenylene) -6,6'-ratio Benzoxazole was used as the active cathode material. The platinum wire was immersed in a methanesulfonic acid solution of 5% benzothiazole polymer to coat a thin film of this polymer and subsequently neutralized in an ethanol / triethylamine bath. The second platinum wire was coated with a thin film of bibenzoxazole polymer in the same manner. The wire positive electrode coated with this benzothiazole polymer and the wire negative electrode coated with the bibenzoxazole polymer were immersed in an acetonitrile solution of 0.1 mol of tetraethylammonium-tetrafluoroborate. This battery was charged with a 4.2 volt battery. This charged cell exhibited an open circuit voltage of 4.0 volts. This battery was then discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 4.2 volts per hour.

Example 11

Platinum / Poly-2,6- (4-phenylquinoline) / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,2 '-(meth-phenylene) -6,6'-bibenzoxazole / Platinum cells were combined, but the poly-2,6- (4-phenylquinoline) polymer was used as the active cathode material, and the bibenzoxazole polymer was used as the active anode material. The platinum wire was immersed in a 5% meta-cresol / phosphorus pentoxide solution of poly-2,6- (4-phenylquinoline) to cover the thin film of this polymer and subsequently neutralized in an ethanol / triethylamine bath. The second platinum wire was coated with a thin film of bibenzoxazole polymer in the manner described in Example 6. The wire positive electrode coated with the quinoline polymer and the wire negative electrode coated with the bibenzoxazole polymer were immersed in an acetonitrile solution of 0.1 mol of tetraethylammonium tetrafluoroborate. The cells thus treated were charged with 4.2 volt batteries. The charged cell exhibited a 3.8 volt open circuit voltage. The battery was discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 3.8 volts per hour.

Example 12

Platinum / poly-para-phenylene-2,5- (1,3,4-oxadiazole) / tetraethylammonium-tetrafluoroborate, acetonitrile / poly (N-methylphenothiazine) -2,5 Combine-(1,3,4-oxadiazole) / platinum cells with poly-phenylene-2,5- (1,3,4-oxadiazole) as the active cathode material and poly (N-methylfe Northiazine) 2,5- (1,3,4-oxadiazole) was used as the active anode material. The platinum wire was immersed in a 5% sulfuric acid solution of poly-para-phenylene-2,5- (1,3,4-oxadiazole) to be covered with a thin film of this polymer. Then neutralized in ethanol / triethylamine bath. The second platinum wire was coated with a thin film of poly- (N-methylphenothiazine) -2,5- (1,3,4-oxadiazole) in the same manner. The wire positive and negative electrodes coated with both polymers were immersed in 0.1 mol of acetonitrile solution of tetraethylammonium-tetrafluoroborate. The battery was then charged with a 3.0 volt battery. The charged cell exhibited an open circuit voltage of 2.7 volts. The cell was discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 2.7 volts per hour.

Example 13

Platinum / poly-para-phenylene-2,5- (1,3,4-oxadiazole) -para-phenylene-2,5- (1,3,4-thiadiazole) copolymer / tetraethyl Combine ammonium-tetrafluoroborate, acetonitrile / poly-2,2 '-(meth-phenylene) -6,6'-bibenzoxazole / platinum cells with poly-para-phenylene-2,5- The (1,3,4-oxadiazole) -para-phenylene-2,5- (1,3,4-thiadiazole) copolymer is an active cathode material and a bibenz oxazole polymer is an active anode material. It was set as.

The platinum wire was immersed in 5% sulfuric acid solution of the copolymer to be covered with a thin film of the polymer and subsequently neutralized in an ethanol / triethylamine bath.

The second platinum wire was allowed to be coated with a thin film of bibenzoxazole polymer by the method described in Example 10. The wire positive and negative electrodes coated with both polymers were immersed in an acetonitrile solution of 0.1 mol of tetraethyl ammonium-tetrafluoroborate. The battery was charged with a 4.0 volt battery. The charged cell exhibited an open circuit voltage of 3.5 volts. The battery was discharged in a short circuit and subsequently recharged. The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 3.5 volts per hour.

Example 14

Platinum / Poly-2,6- (4-phenylquinoline) / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole Combine / platinum batteries with poly-2,6- (4-phenylquinoline) as the active cathode material and poly-2,2 '-(para-phenylene) -6,6'-bibenz oxazole active cathode It was made into a substance. The platinum wire was immersed in a 5% meta-cresol / phosphorus pentoxide solution of poly-2,6- (4-phenylquinoline) to be covered with a thin film of this polymer. Subsequently neutralized in ethanol / triethylamine bath. The second platinum wire was coated with a thin film of bibenzoxazole polymer by the method described in Example 6. Two polymer coated wire positive and negative electrodes were immersed in a solution of acetonitrile of 0.1 mol of tetraethyl ammonium-tetrafluoroborate. The charged cell exhibited an open circuit voltage of 3.1 volts. The battery was discharged in a short circuit and subsequently recharged. The battery was repeatedly charged and discharged several times in this manner to obtain an open circuit voltage of 3.1 volts per hour. The coulomb efficiency of this charge and discharge process was 30%. This battery was repeatedly recharged within the range of laboratory error to 30% of its original capacity.

Example 15

Platinum / poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole / tetraethylammonium-tetrafluoroborate, acetonitrile / poly-2,2'-(para-phenylene ) -6,6'-bibenzoxazole / platinum cells were combined, but poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole was used as the active positive electrode material and the active negative electrode material. . Two platinum wires were immersed in a 5% methanesulfonic acid solution of the bibenzoxazole polymer to be coated with a thin film of this polymer. Subsequently neutralized in ethanol / triethylamine bath. The wire positive and negative electrodes coated with two polymers were immersed in a solution of acetonitrile of 0.1 mol of tetraethyl ammonium-tetrafluoroborate. Such a battery was charged with a 3.5 volt battery. The charged cell exhibited an open circuit voltage of 3.3 volts. The battery was discharged in a short circuit and subsequently recharged.

The battery was charged and discharged several times in this manner to obtain an open circuit voltage of 3.3 volts per hour.

The coulomb efficiency of the charging and discharging process was 30%.

Within the range of laboratory error, the cell was repeatedly recharged to 40% of its original capacity.

Claims (43)

A cell consisting of a negative electrode and a positive electrode, a separator separating the positive electrode and the negative electrode, and a case coupled with an electrolyte, wherein at least one of the electrodes is a current collector and a linear, easily handled, electrically active polymer. This polymer is a linearly charged polymer with a mixture of ionic semifluids that replenish the charge, and can simultaneously cause reverse oxidation, reverse reduction, reverse oxidation, and reverse reduction, and the polymer can contain none of the ring carbon atoms. A heterocyclic ring system comprising at least one group 5B or 6B atom that is not saturated, and a complex containing at least one group 5B or group 6B atom in which none of the ring carbon atoms is saturated or not a linking unit A repeating group of a double group selected from the group consisting of a cyclic ring system and a mixture of these heterocyclic ring systems Wherein the repeating unit of the double group in the form of the repeating unit of the monomer may simultaneously cause reverse oxidation, reverse reduction, or reverse oxidation, reverse reduction to be a stable ionizing material, wherein the linking unit is a heterocyclic ring Wherein said cell is an airspace system or atom or group of atoms that maintains a [pi] orbit overlapping the system. A cell according to claim 1, wherein the 5B or 6B heteroatoms are nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium or mixtures thereof. A cell according to claim 2, wherein none of the heteroatoms occupies a ring fusion site. A cell according to claim 3, wherein the dual atoms composed of atomic groups phosphorus, arsenic, oxygen, sulfur, selenium and tellurium do not occupy contiguous ring positions. A cell according to claim 3 wherein the heteroatoms are selected from atomic groups consisting of nitrogen, sulfur, oxygen or mixtures thereof. Consisting of thiasrene, phenoxasri, phenoxazine, N-alkylphenothiazine, dihydrophenazine, dialkyl-dihydrophenazine, dibenzodioxin, substituted derivatives thereof and mixtures thereof A cell according to claim 5 which is a double group in position selected from the atomic group. The cell according to claim 5, wherein the double group is a positional double group selected from the group of atoms consisting of benzoxazole, benzothiazole, benzo selenazole, N-alkyl-substituted benzimidazole, substituted derivatives thereof and mixtures thereof. Dual groups 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 '] bis selenazole , Benzo [1,2-d: 5,4-d '] bistelurazole, selenazolo [5,4-f] benzothiazole, 1,8-dialkyl-benzo [1,2-d: 3 , 4-d '] diimidazole, benzo [1,2-d: 5,4-d'] bisoxazole, benzo [1,2-d: 4,5-d '] bisoxazole, benzo [ Position selected from the group consisting of 1,2-d: 3,4-d '] bisoxazole, benzo [1,2-d: 3,4-d'] bisthiazole, substituted derivatives thereof and mixtures thereof A cell according to claim 5 which is a double group on a substrate. The cell according to claim 5, wherein the double group is selected from atomic groups consisting of all the above double groups, each of which is trivalent, thiadiazole, oxadiazole, oxazole and diazole, 1,4-phenylene. The cell according to claim 5, wherein the hetero atom is nitrogen and the nitrogen atom within the field is continuously bonded in a heterocyclic ring system. Dual groups are cinnoline, quinazoline, quinoxaline, 2-phenylquinoxaline, phthalazine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine, 2, 6-naphthyridine, kopirin, 1,2,4-benzotriazine, pyrido [3,2-d] pyrimidine, pyrido [4,3-d] pyrimidine, pyrido [3,4-d ] Pyrimidine, pyrido [2,3-d] pyrimidine, pyrido [2,3-b] pyrazine, pyrido [3,4-d] pyrazine: pyrido [2,3-d] pyridazine, Pyrido [3,4-d] pyridazine, pyridazino [4,5-c] pyridazine, pyrimido [5,4-d] pyrimidine, pteridine, pyrimido [4,5-d] Pyridazine, pyrimido [4,5-d] pyrimidine, 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] -s-triazine, pyrimido [4,5-e]- S-triazines and pyrido [2,3-e] s-triazines and es-triazino [6,5-d] estrias selected from atomic groups A cell according to claim 10 which is a double group in position. The cell according to claim 10, wherein the polymer consists of a double group unit in the positional double groups of quinoline, isoquinoline, quinoxaline, wherein the double groups are polymers dotted with linking units and their substituted derivatives or mixtures thereof. . The solvent of the electrolyte solution is selected from atomic groups consisting of acetonitrile, polypropylene carbonate, tetra hydrofuran, propionitrile, butyronitrile, phenylacetonitrile, dimethylformamide, dimethoxyethane, dimethylsulfoxide, pyridine or mixtures thereof A cell according to claim 1. The secondary electrolyte cations dissolved in the solvent are Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ⁺⁺ , (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , (C ₃ H ₇ ) ₄ or N ⁺ _{(C 4 H 9) 4 N} + a is selected from the group of atoms consisting of the anion is ^{F -, Cl -, Br -} , I -, CIO 4 -, BF 4 -, PF 6 -, AsF 6 -; Or a salt selected from an atomic group consisting of a cation-anion pair selected from the atomic group consisting of NO ₃ ⁻ . The polymer forms a positive electrode and the negative electrode consists of a material with a redox potential in an electrolyte solution that is more positive than the redox potential of the polymer, the negative electrode of which is one of the metal, its slightly soluble anionic salts. A metal coated with a layer of, a polymer different from the positive electrode, which can insert ions present in the polymer or electrolyte solution having a redox potential in an electrolyte solution that is more positive than the redox potential difference of the positive electrode polymer. A cell according to claim 14 consisting of: Anode is poly-2,2 '-(para-phenylene) -1,1'-dimethyl-5,5'-dibenzimidazole, poly-2,2'-(para-phenylene) -5,5 '-Bibenzoxazole, poly-2,2'-(para-phenylene) -5,5'-bibenzthiazole, poly-2,6- (para-phenylene) -benzo [1,2- d: 5,4-d '] bisoxazole, poly-2,6- (para-phenylene) -1,7-dimethyl-benzo [1,2-d: 4,5-d] diimidazole, Poly-2,6- (para-phenylene) -benzo [1,2-d: 4,5-d '] bisthiazole, poly-2,6- (meth-phenylene) benzo [1,2-d : 4,5-d '] bisthiazole, poly-1,4-phenylene 2,5- (1,3,4-oxadiazole); Copolymer of oxadiazole and thiadiazole with 1,4-phenylene linking unit, copolymer of oxadiazole and thiadiazole, poly-1,4-phenylene-2,5- (1,3,4 -Thiadiazole), poly-1,4-phenylene-2,4- (1,3-thiazole), poly-1,4-phenylene-2,5- (1-phenyl-1,3, 4-triazole), poly-1,4-phenylene-2,5- (1,4-ditin); A cell according to claim 15 which is a polymer selected from the group consisting of poly-2,6- (4-phenylquinoline) and poly-2,6- (4-phenylquinoline) combined with a bonding unit. Cathode is poly-2,2 '-(meth-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(meth-phenylene) -1,1'-dimethyl-6,6 '-Bibenz-imidazole, poly-2,2'-(meth-phenylene) -6,6'-bibenzthiazole, poly-2,2 '-(N-methyl-P, P'-amino Diphenylene) -6,6'-bibenzoxazole, poly-2,5-phenoxazine, poly-2,5 '-(3,7-dimethyl) phenoxazine, poly-2,5- (1, 4-phenylene) phenoxazine, poly-3,7 (N-methylphenothiazine) -2,5- (1,3,4-oxadiazole), poly-3,7- (phenoxatiin- 4,4'-dithiobiphenylene) -poly- (1,4-dithiophenylene-2,6-thiaxene) and poly-4,4'-N-methyl-aminodiphenylene) -2, A cell according to claim 16 which is a polymer selected from atomic groups consisting of 5- (1,3,4-oxadiazoles). The cell according to claim 16, wherein the negative electrode is polyacetylene, polypyrrole, polyphenylenesulfide, polyphenylene, poly-1,6-heptadiene, or mixtures thereof. The cell according to claim 16, wherein the negative electrode is a polymer in the N-alkylated form of the positive electrode and the N-alkylated polymer has a redox potential that is more positive than the redox potential of the positive polymer. The polymer forms a cathode and the roots are composed of a material with a redox potential in an electrolyte solution that is more negative than the redox potential of the polymer, the anode being one layer of a metal, its slightly soluble anion salt. Metal coated with a negative electrode, a polymer different from the negative electrode, and composed of a polymer having a redox potential in an electrolyte solution having a negative potential lower than that of the negative electrode polymer, or an insertion compound capable of inserting ions present in the electrolyte solution A cell according to claim 14, wherein Cathode was poly-2,21- (meth-phenylene) -6,6'-bibenzoxazole, poly-2,2 '-(meth-phenylene) -1,1'-dimethyl-6,6' -Bibenzimidazole, poly-2,2 '-(meth-phenylene) -6,6'-bibenzthiazole, poly-2,2'-(N-methyl-P, P'-aminodiphenyl Ren) -6,6'-bibenzoxazole, poly-2,5-phenoxazole, poly-2,5 '-(3,7-dimethyl) phenoxazine, poly-2,5- (1,4 -Phenylene) phenoxazine, poly-3,7- (N-methyl-phenothiazine) -2,5- (1,3,4-oxadiazole-poly-3,7) -phenoxadiin- 4,4'-dithiophenylene, poly- (1,4-dithio-phenylene-2,6-thianesrene), poly-4,4'-N-methylaminodiphenylene-2,5- (1,3,4-oxadiazole), poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(para-phenylene)- Claims which are polymers selected from atomic groups consisting of 6,6'-bibenz-thiazole and poly-2,2 '-(para-phenylene) -1,1'-dimethyl-6,6'-bibenzimidazole The cell according to claim 20. The polymer forms a positive electrode and the negative electrode consists of a material having a redox potential in an electrolyte solution that is more positive than the redox potential of the polymer, and the negative electrode is a metal capable of electroprecipitation into the electrolyte solution, and vice versa A polymer coated with one layer of its slightly soluble ionic salt which can cause oxidative and reversely oxidizable positive electrode polymers and different polymers, oxidizing in an electrolyte solution that is more positive than the redox potential of the positive electrode A cell according to claim 1, consisting of a polymer having a reducing potential or an auxiliary electrolyte present in an electrolyte solution which can be inserted inversely. Polymer

Where Z is a linking unit or absent;

Poly-2,2 '-(para-phenylene) -1,1'-dimethyl-5,5'-bisbenz-imidazole, poly-2,2'-(para-phenylene) -5,5 ' -Bibenzoxazole, poly-2,2 '-(para-phenylene) -5,5'-bibenzthiazole, poly-2,6- (para-phenylene) -benzo [1,2-d : 5,4-d '] bisoxazole, poly-2,6- (para-phenylene) -1,7-dimethyl-benzo [1,2-d: 4,5-d'] diimidazole, Poly-2,6- (para-phenylene) -benzo [1,2-d: 4,5-d '] bisthiazole, poly-2,6- (meth-phenylene) benzo [1,2-d : 4,5-d '] bisthiazole, poly-1,4-phenylene-2,5- (1,3,4-oxadiazole), oxadiazole and thiadiazole with 1,4-phenylene Copolymers with binding units, copolymers of oxadiazoles and thiadiazoles, poly-1,4-phenylene-2,5- (1,3,4-thiadiazole), poly-1,4-phenyl Lene-2,4- (1,3-thiazole), poly-1,4-phenylene-2,5- (1-phenyl-1,3,4-triazole) and poly-1,4-phenyl A cell according to claim 12 selected from an atomic group consisting of len-2,5- (1,4-dithiene). R _III is hydrogen, an alkyl group of 1-4 carbon atoms, an alkoxy group of 1-4 carbon atoms, an alkylthio group of 1-4 carbon atoms, a cyclic aliphatic atom group of 5 or 6 carbon atoms, a cyclic aliphatic of 2-4 carbon atoms Atomic groups, alkenyl atom groups of 2-4 carbon atoms, aryl atom groups of 6-10 carbon atoms, aryl atom groups of 6-10 carbon atoms substituted by 1-3 alkyl atoms of 1-4 carbon atoms, 1-4 Alkenyl atom group of carbon atoms, Alkynyl atom group of 1-4 carbon atoms, Alkoxy atom group of 1-4 carbon atoms, 1-3 cyano atom groups, 1-3 halogen atom groups, Dialkylamino atom groups of 1-4 carbon atoms And a substituent atom group selected from alkylthiol of 1-4 carbon atoms, containing 5 or 6 membered nitrogen, unsaturated heterocyclic atom group, R _VII is hydrogen or CH ₃ , and the positive electrode according to claim 22 having the structure battery.

The negative electrode is silver, iron, copper, zinc, nickel, palladium, tin or mixtures thereof, and the cell has an ion selective membrane separating the cell into a positive electrode and a negative electrode, and the membrane has a metal ion to the anode chamber. A cell according to claim 23 which prevents diffusion and spread at the anode. The cell according to claim 23, wherein the negative electrode is silver halide or a metal silver coated with a layer of an intercalating compound of LixTiS _{2 with} X of 0 to 1. The negative electrode is poly-2,2 '-(meth-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(meth-phenyl) -1,1'-dimethyl-6,6 ' -Bibenzimidazole, poly-2,2 '-(meth-phenylene) -6,6'-bibenzthiazole, poly-2,2'-(N-methyl-P, P'-aminodiphenyl Ren) -6,6'-bibenzoxazole, poly-2,5-phenoxazine, poly-2,5 '-(3,7-dimethyl) -phenoxazine, poly-2,5- (1,4 -Phenylene) phenoxazine, poly-3,7- (N-methyl-phenothiazine) -2,5- (1,3,4-oxadiazole), poly-3,7- (phenoxadiin -4,4'-dithiobiphenylene), poly- (1,4-dithio-phenylene-2,6-thianesrene), poly-4,4'-N-methylaminodiphenylene-2, 5- (1,3,4-oxadiazole), poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(para-phenylene ), 6,6'-bibenz-thiazole and poly-2,2 '-(para-phenylene) -1,1'-dimethyl-6,6'-bibenzimidazole The cell according to claim 23, which is a P-type polymer. The polymer forms a negative electrode, and the positive electrode consists of a material with a redox potential in an electrolyte solution that is more negative than the polymer's redox potential, which is oxidized to the metal that can be electroprecipitated into the electrolyte solution, and vice versa. And a polymer different from the positive electrode polymer that can be oxidized and the reversely oxidized positive electrode polymer coated with one layer of its slightly soluble anionic salt, which can be reduced, in an electrolyte solution that is more positive than the redox potential of the positive electrode. A cell according to claim 1 consisting of an intercalating compound capable of reversely intercalating a secondary electrolyte ion present in a polymer or electrolyte solution with a reduction potential. The negative electrode is poly-2,2 '-(meth-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(meth-phenylene) -1,1'-dimethyl-6,6 '-Bibenzimidazole, poly-2,2'-(meth-phenylene) -6,6'-bibenzthiazole, poly-2,2 '-(N-methyl-P, P'-aminodi Phenylene) -6,6'-bibenzoxazole, poly-2,5-phenoxazine, poly-2,5 '-(3,7-dimethyl) -phenoxazine, poly-2,5- (1, 4-phenylene) phenoxazine, poly-3,7- (N-methyl-phenothiazine) -2,5- (1,3,4-oxadiazole); Poly-3,7- (N-methylphenothiazine) -2,5- (1,3,4-oxadiazole), poly-3,7- (feoxadiin-4,4'-dithiobi Phenylene), poly- (1,4-dithio-phenylene-2,6-thiaxene), poly-4,4'-N-methylaminodiphenylene-2,5- (1,3,4 -Oxadiazole), poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(para-phenylene) -6,6'-ratio Claim 28 which is a reversible P-type polymer selected from atomic groups consisting of benz-thiazole and poly-2,2 '-(para-phenylene) -1,1'-dimethyl-6,6'-bibenzimidazole Battery according to claim. The cell according to claim 29, wherein the positive electrode is selected from atomic groups consisting of lithium, sodium, potassium, rubidium, cesium or alloys thereof and intercalating compounds of LixWO ₂ with X of 0 to 1. The positive electrode is poly-2,2 '-(para-phenylene) -1,1'-dimethyl-5,5'-bibenz-imidazole, poly-2,2'-(para-phenylene) -5, 5'-bibenzoxazole, poly-2,2 '-(para-phenylene) -5,5'-bibenzthiazole, poly-2,6- (para-phenylene) -benzo [1,2 -d: 5,4-d '] bisoxazole, poly-2,6- (para-phenylene) -1,7-dimethyl-benzo [1,2-d: 4,5-d'] diimi Dazole, poly-2,6- (para-phenylene) -benzo [1,2-d: 4,5-d '] bisthiazole, poly-2,6- (m-phenylene) benzo [1,2 -d: 4,5-d '] bisthiazole, poly-1,4-phenylene-2,5- (1,3,4-oxadiazole), oxadiazole and thiadiazole and 1,4- Copolymers with phenylene bond units, copolymers of oxadiazole and thiadiazole, poly-1,4-phenylene-2,5- (1,3,4-thiadiazole), poly-1,4 -Phenylene-2,4- (1,3-thiazole), poly-1,4-phenylene-2,5- (1-phenyl-1,3,4-triazole) and poly-1,4 -Phenylene-2,5- (1,4-dithiene), poly-2,6- (4-phenyl-quinoline) and poly-2,6- (1,4-dithiene), poly-2, 6- (4-phenyl-quinoline) and poly-2,6- (4-phenyl-quinol The cell according to claim 29, which is a reversible n-type polymer selected from the group of atoms consisting of formulating a binding unit in rin). The negative electrode and the positive electrode are poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole, poly-2,2'-(para-phenylene) -6,6'-bibenztia Claims which are reversible n-type and p-type polymers selected from atomic groups consisting of sol and poly-2,2 '-(para-phenylene) -1,1'-dimethyl-6,6'-bibenz-imidazole The battery according to claim 1. The cell according to claim 22, wherein the negative electrode consists of polypyrrole and the positive electrode consists of poly-2,6- (4-phenylquinoline). The cell according to claim 26, wherein the negative electrode consists of silver halide and the coated silver and the positive electrode consists of poly-2,6- (4-phenylquinoline). The cell according to claim 30, wherein the positive electrode is lithium and the negative electrode is poly-2,6- (4-phenylquinoline). The cell according to claim 31, wherein the negative electrode is poly-2,5-phenoxazine and the positive electrode is poly-2,6- (4-phenylquinoline). The cell according to claim 31, wherein the negative electrode is poly-2,6-N-methyl- (4-phenylquinoline) and the positive electrode is poly-2,6- (4-phenylquinoline). The cell according to claim 31, wherein the negative electrode is poly-2,5-phenoxazine and the positive electrode is poly-2,2 '-(para-phenylene) -6,6'-bisbenzoxazole. According to claim 31, wherein the positive electrode is poly-2,6- (para-phenylene) -benzo [1,2-d: 5,4-d '] bisoxazole and the negative electrode is poly-2,5-phenoxazine battery. To claim 31, wherein the negative electrode is poly-2,5-phenoxazine and the positive electrode is poly-2,6- (para-phenylene) -benzo [1,2-d: 4,5-d '] bisthiazole. According to the battery. The cell according to claim 31, wherein the negative electrode is poly-2,5-phenoxazine and the positive electrode is poly-para-phenylene-2,5- (1,3,4-oxadiazole). The negative electrode is poly-2,2 '-(meth-phenylene) -6,6'-bibenzoxazole and the positive electrode is poly-2,6- (para-phenylene) -benzo [1,2-d: 4, 5-d '] The cell according to claim 31, which is bisthiazole. The cell according to claim 32, wherein the positive electrode and the negative electrode are poly-2,2 '-(para-phenylene) -6,6'-bibenzoxazole.