NL8400207A - ELECTRONICALLY CONDUCTIVE POLYOYRROL AND COPYOLYMERS OF PYRROL, COMPOSITIONS CONTAINING THESE POLYMERS OR COPOLYMERS, METHODS FOR PREPARING THESE POLYMERS OR COPOLYMERS AND ELECTRIC CELLS IN WHICH THEY ARE USED - Google Patents

Description

* 'C

Electronically conductive polyoyrrole and pyrrole copolymers, compositions containing these polymers or copolymers, methods of preparing these polymers or copolymers and electric cells in which they are used.

Technical area

The invention relates to polypyrrole and copolymers of pyrrole. More particularly, the invention relates to electronically conductive compositions containing electropolymerized polypyrrole or a pyrrole copolymer; to methods of preparing electronically conductive polypyrrole or copolymers of pyrrole; and to electrochemical cells containing polymeric electrode members, which polymeric electrode members are positive and / or negative and electronically conduct polypyrrole or a pyrrole copolymer.

Background of the Invention The term polypyrrole refers to polymers containing polymerized pyrrole rings. A pyrrole ring is an unsaturated five-membered ring containing four carbon atoms and a nitrogen atom. Polypyrrole is here not limited to polymers of unsubstituted pyrrole monomer, nor is it limited to polymerization at certain locations in the pyrrole rings. A preferred polypyrrole for use in accordance with the invention is the 2.5 polymerized homopolymer of unsubstituted pyrrole. The term pyrrole copolymer refers to any polymer containing pyrrole and / or substituted pyrrole monomers and / or one or more other monomers which is copolymer therewith.

Polypyrrol belongs to the general class of electronically conductive organic polymers and is more particularly one of the group of polymers which, under certain conditions, are -1 -1 and.

conductivity greater than about 1 ohm cm j which have been developed in recent years. Other well-known members of this group are polyacetylene. poly-p-phenylene, poly-p-phenylene sulfide and poly (2.5 thienylene).

Pyrrole black, a polymeric powder material, prepared by oxidizing pyrrole in homogeneous solution (for example, with Η · 2 ^ 2 ^ has been known for years. Gardini, Adv. Heterocycl. Chem., 15, 10 (1973). An electrochemical method for the preparation of polypyrrole as a powdery film on an electrode has been reported A. Dali 'Olio et al., Comp. Rend., 433, 267c (1968) Electropolymerization for producing polymer films from pyrrol have been reported. ., J. Chem. Soc., Chem.

15 Comm., 635, (1979) (hereinafter Diaz (I); Diaz et al., J. Chem. Soc., Chem. Comm. 397 (1980) (hereinafter Diaz II); Diaz, Chemica Scripta, 17, 45 (1981) (hereinafter Diaz (III); and Kanazawa et al., J. Chem. Soc., Chem. Comm., 954 (1979) (hereinafter Kanazawa (I)). Electro-polymerized polypyrrole from substituted pyrrole is reported Diaz (II), Diaz et al., J. Eketroanal Chem., 129, 115, (1981) (hereinafter Diaz (IV)), Diaz et al., J. Eletroanal Chem., 130, 181 (1981) (hereinafter Diaz (V)) Copolymer films made by electropolymerizing mixtures of pyrrole and substituted pyrrole have also been reported A mixture of pyrrole and N-methylpyrrole has been polymerized and it is believed that both monomers in the polymer are Diaz (II); Diaz, Proc Int Conf on Low Dimensional Synthetic Metals Chemica Scripta, 17, 0000, (1981) (hereinafter Diaz (VI)); and Kanazawa et al.

J. Synth. Metals, £ 119 (1981) (hereinafter Kanazawa (II)).

Polypyrrol is electronically conductive in the charged or oxidized state (black) and is prepared in this state by electropolymerization. When it is completely reduced 8400207 *, »i m

* I

- 3 - up to neutral or cratledea state (yellow), it is an electronic insulator. The electropolymerized polypyrrole is prepared in the oxidized, i.e., gradual, state and (unlike other conductive polymers such as polyacetylene), no flocculating chemical or electrochemical treatment is required to increase the conductivity above 1 ohm * cm *. A counter anion is incorporated into the material during the electropolymerization process to balance the positive charge on the polymer hull. Diaz (III).

Polypyrrol can be prepared as powders. Gardini see above. Polypyrrole can also be electro-polymerized as a continuous film on electrodes. The highest electronic conductivities reported for the continuous films are on the order of about 100 ohm-cm-Diaz (I); Kanazawa and 15 raedew., Syn. Metals, J ^. 329, (1980) (hereinafter Kanazawa (III)). These conductivities can be orders of magnitude lower depending on the counter anion incorporated.

A large number of counter anions have been used, including BF ^, PFg, AsFg, C10 ^, HSO ^, CFgSO ^, CH ^ CgH ^ SO ^, 20 CF ^ COO. , 'ΒΚ ^ Οή. Fe (CN) g ^. Diaz (IV); Diaz (VI); Kanazawa (I) and Noufi et al., J. Electrochem. Soc., 128, 2596 (1981).

N-substituted pyrrole are polymerized, including methyl, ethyl, n-propyl, η-butyl, isobutyl and phenyl, and substituted phenylpyrrole. Diaz (IV); Diaz et al., Elec-25 Trochemical Society Extended Abstracts, Vol. 82-1. Abstract No.

617, (1982) (hereinafter Diaz (VII)). Electronic conductivities of these sizes have been reported orders of magnitude less than that of the polypyrrole itself. Kanazawa (II); Diaz (VII).

Beta-substituted pyrrole, such as 3,4-30 dimethylpyrrole, have been reported to be polymerized. Gardini, see above.

The polymers have been prepared to date with non-aqueous solvents, typically acetonitrile, (Diaz (I); Diaz (II); 3400207-4 and Diaz (VI)), which are dissolved. salt, which contains the counter anion. It is known that the physical properties of the. films obtained are sensitive to the forming conditions. For example, in acetonitrile, small traces of water in the solvent form a film with smoother surfaces than is obtained in anhydrous acetonitrile. Diaz (VI). The polypyrrole tetrafluoroborate films ,. prepared by Diaz and co-workers are continuous, space-filling ... and very poorly crystalline with a density of 1.48 g cm.

Kanazawa (III).

Polypyrrole films are thermally stable at room temperature and are insoluble in the usual solvents. Diaz (I) '; Kanazawa (II); and Tourillon et al., Electrochemical i

Society Extended Abstracts, Vol. 82-1, Abstract No. 618, (1982). Polypyrrole in the oxidized form has been reported to be chemically stable at ambient conditions of O2 and moisture for several months. Diaz et al., J. Eletroanal. Chem., 121, 355, (1981) (hereinafter Diaz (VIII)); Watanabe et al., Bull. Chem. Soc. Jpn., 54, 2278 (1981). Polypyrrole fluoroborate films have been found to be unstable under oxidative conditions, such as potentials greater than +0.6 V (SCE) or in the presence of halogens. Bull et al., J. Electrochem., Soc., 129, 1009. (1982).

Polypyrrol can be repeatedly driven between the conductive and non-conductive states. Bull and co, supra; Diaz et al., "Conducting Polymers", Polymer Sci. & Technology, 25, 149 et seq., Plenum Press, N.Y., (1981) (hereinafter Diaz (IX)). It has been reported that rapid full switch using thin films (i.e., less than about 0.1 µm) and switching is difficult at thicknesses greater than about 1 µm. Diaz (II);

Diaz (IX). It has been shown that although a film may contain BF ^ counter anions 30 when it is formed (i.e. in the charged state) BF ^ is no longer present in the film when it is in neutral state (i.e. reduced or discharge 8400207 ml: "% - 5 position). Diaz (IV). They have suggested that both anion and fcation of the electrolyte salt affect ion diffusion during reduction and oxidation of polypyrrole films. Diaz (IV).

Polymers have been prepared with different degrees of oxidation, depending on the anion and / or substituents. Most of these materials have degrees of oxidation around 0.25 (i.e. a quarter of the polymer rings are oxidized).

Summary of the invention 10

The compositions of the invention are electronically conductive compositions containing an electro-polymerized polypyrrole or pyrrole copolymer, and these compositions may be either porous or non-porous materials in the form of films, powders, dendriform materials, in various shapes, as desired manufactured by pressing powders of the compositions of the invention. These compositions are particularly suitable for the manufacture of positive and / or negative polymer electrodes for use in electrochemical cells such as, for example, electrochemical energy storage cells.

The object of the invention is to provide a porous electronically conductive composition containing an electro-polymerized polypyrrole or copolymer of pyrrole, which composition is characterized by an apparent density of about 0.01 g cm to the apparent density. of the polypyrrole or copolymer and an area of at least twice the area of a smooth film of apparent density of the composition. The invention further provides an electrochemical cell containing polymeric electrode members, which polymeric electrode members are positive and / or negative and which contain the composition described above.

The invention furthermore provides an electronic 8400207 * * - 6 - conductive composition, comprising electro-polymerized polypyrrole or a copolymer of pyrrole, which composition contains one or more low-mobility anions and is characterized by an average ionic transport number of the low-mobility anions 5 during reduction less than about 0.1. The invention further provides an electrochemical cell containing polymeric electrode members, which polymeric electrode members are positive and / or negative and which contain the aforementioned composition.

The object of the invention is furthermore to provide a method for preparing electronically conductive polypyrrole or copolymer and of pyrrole, which comprises electropolymer agents of pyrrole or a copolymerizable mixture containing pyrrole, ... on a electronically conductive surface in an electrolytic bath, the method comprising the steps of: (A) dipping an electronically conductive surface in an electrolytic bath containing at least one liquid and at least one immiscible liquid or gas or finely divided solid particles wherein the pyrrole or the copolymerizable mixture containing a pyrrole is one of the liquids or is dissolved in at least one of the liquids and (B) passes an electric current through the bath at a voltage sufficiently is for electropolymerizing the pyrrole or copolymerizable mixture containing a pyrrole on the electronically conductive surface. In a preferred embodiment of this method, the electrolytic bath contains an aqueous mixture containing pyrrole or a mixture of pyrrole and a copolymerizable monomer and water. The invention further provides an electrochemical cell containing polymeric electrode members, which polymeric electrode members are positive and / or negative and contains electronically conductive pyrrole or a copolymer of pyrrole prepared according to the method described above.

Furthermore, the invention provides a method of preparing electronically conductive polypyrrole or a copoly-8400207.

φν ίft »- 7 - More of pyrrole, which comprises the steps of: (A) electropolymerizing a pyrrole or a copolymerizable mixture of pyrrole on an electronically conductive surface in an electrolytic bath by (1) immersing an electronically conductive surface in 5 an electrolytic bath containing (a) an aqueous dispersion of a pyrrole or a mixture of the aqueous dispersion and at least one copolymerizable monomer or (b) a pyrrole or mixture of a pyrrole and / or at least one copolymerizable monomer, water and a water immiscible diluent, (2) stirring the bath and (3) passing an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or pyrrole mixture and deposit the polymer or copolymer on the electronically conductive surface, and (B) removing the polymer or copolymer from the conductive surface.

In a preferred embodiment of this method, the electrolytic bath contains an aqueous mixture containing pyrrole or a copolymerizable mixture of pyrrole, water and one or more low-mobility anions, which are incorporated into the polypyrrole by electropolymerization and which are characterized by anions by an average ionic transport number for the less mobile anions at reduction less than about 0.1. The invention further provides an electrochemical cell containing polymeric electrode members, which polymeric electrode members are positive and / or negative and contain polypyrrole or a pyrrole copolymer prepared according to the method described above.

Furthermore, the invention provides a method of preparing an electronically conductive polypyrrole or a copolymer of pyrrole, which comprises electropolymerizing a pyrrole isable or a copolymer mixture containing a pyrrole on an electronically conductive surface in an electrolytic bath. by (A) immersing an electronically conductive surface in an electrolytic bath containing (1) a pyrrole or a mixture of a pyrrole 3400207-8 with a copolymerizable monomer (2) one or more little mobile anions, which are in the polypyrrole or pyrrole copolymer which are characterized by an average ionic transport number of the low-mobility anions during reduction of the polypyrrole or copolymer less than 0.1, and (3) an organic diluent, and (B) feeding an electric current through Met bath at a voltage sufficient to electro-polymerize the pyrrole or copolymerizable mixture containing pyrrole, o p the electronically conductive surface. The invention further provides an electrochemical cell containing polymeric electrode members, which polymeric electrode members are positive and / or negative and which contain polypyrrd-laE a copolymer of pyrrole prepared by the methods described above.

15 Brief description of the drawing

Figure 1 is a side view of a laboratory scale lithium cell illustrating the invention in some form.

Figure 2 is a side view of a laboratory scale electrochemical cell illustrating another embodiment of the invention in some form.

Figure 3 is a perspective view of an electrochemical energy storage cell. illustrating another embodiment of the invention in a particular form.

Figure 4 is a side view of the electrochemical cell shown in Figure 3.

Figure 5 is a side view of an electrochemical energy storage cell, illustrating another embodiment of the invention in some form.

Figure 6 is a side view of a layered or stacked electrochemical energy storage cell, illustrating another embodiment of the invention in a particular form; and

Figure 7 is a side view of a layered or stacked electrochemical energy storage cell, illustrating yet another embodiment of the invention in some form.

Description of the Preferred Embodiments

In a preferred embodiment of the invention, the electronic conductive compositions of the invention contain at least one slightly mobile, anion, A, which has a strong tendency to be retained in the composition upon reduction. The transport of ionic charge to compensate for the change in oxidation state of the polymer 15 then mainly takes place through ions of the electrolyte in which the redox process is carried out. The low-mobility anions can be characterized by their ionic transport numbers. The ionic transport number is defined as the fraction of the ionic current transported by the determined anion averaged over almost complete reduction of the composition.

The polymer is formed in the oxidized state (black), which is electronically conductive, and can be reduced to the neutral state (yellow), which is insulating. For practical purposes, the reduction of thick (500 millimicron or 25 more) films does not fully convert, even at very negative potentials.

The material remains black in appearance and retains some electronic conductivity, although above about 90% reduction its resistance may increase. Generally, the low-mobility anions introduced into the composition of the invention will be characterized by an average ionic transport number for the low-mobility anions during reduction of less than 0.1 and preferably less than about 0.05. The 8400207-10 - most preferred low-mobility anion is an anion characterized by an average ionic transport number for the low-mobility anions during reduction less than 0.01.

These transport numbers can be determined by elementary analysis of the polymers before and after reduction. The transport number (t ^) of the low-mobility anion can be defined as follows: tA - ana / (na) 0 10 compensates for that where (N.) n is the number of molecules of the charge, which anion1 initially in the polymer ia (when this in the geoxy-

third state) and ΔΝ. is the change in the number of mill it, A.

van, 'anion na; ·. :: almost complete reduction (against the neutral state).

The porous compositions of the invention are also characterized by an apparent density of about 0.01 g -3 cm to about the bulk density of the polypyrrole or copolymer of pyrrole.

20

Bulk or theoretical density of the polymers is the density of continuous, pure polymer, which does not contain voids, pores, voids or inclusions. The bulk or theoretical density can usually be determined by flotation methods. Apparent density for less dense forms of the polymer, such as the porous materials, is determined from the mass of the polymer and the volume, calculated from the external dimensions of the material. Since voids, voids, etc. are present in the porous material type, their apparent density will be less than the bulk density.

30. ....

The porous composition of the invention is also characterized in that it has an electrochemically accessible surface of at least twice the surface of a smooth 8400207 film with bulk density of the polymer or copolymer. Preferred materials have significantly large areas (e.g., 1000 times or more than a bulk density smooth film).

The electronically conductive compositions of the invention contain either polypyrrole or polypyrroles or copolymer or copolymers of pyrrole, which can be obtained by (a) polymerizing mixtures of a pyrrole with other copolymerizable monomers or (b) grafting a comonomer or comonomers a polypyrrole polymer or by (c) grafting a pyrrole monomer or monomers onto a preformed polymer based on a monomer other than pyrrole.

The pyrrole monomers, which can be electro-polymerized, are pyrrole or substituted pyrrole, such as N-substituted or C-substituted pyrrole, as described more fully below. Homopolymers of these pyrrole and preferably the homopolymers of unsubstituted pyrrole are included.

Copolymers of a pyrrole can be prepared, for example, by polymerizing a mixture of pyrrole and one or more substituted pyrrole, which may be substituted either on the nitrogen atom or on one or more of the ring carbon atoms in the beta position. Preferably, the substituent is a lower alkyl group of 1 to 7 carbon atoms, most preferably a methyl group. Thus, for example, copolymers of pyrrole and N-methylpyrrole or 3,4-dimethylpyrrole can be prepared according to the methods of the invention. Alternatively, pyrrole can be copolymerized with other heterocyclic ring compounds, including those containing nitrogen (e.g. pyridine, aniline, indole, etc.), furan and thiophene, or with other aromatic or substituted aromatic compounds.

The low mobility anions included in the compositions of the invention can be either organic or inorganic anions. Examples of little 8400207? Mobile inorganic anions which can be used in the invention include transition metal complexes such as ferricyanide, nitroprusside, iron / sulfur cluster compounds such as the redox centers of the rubredoxins and ferridoxins, boron cluster compounds, cobalt hexacyanide, other transition metal nitroprlex splexide complex transition metal oxy complexes or sulfides and chalcogenide complexes, e.g. WO ^, MoO ^, Mo (CN) g,

Fe ^ S ^ C ^ Hj2> CrO, etc.

Preferably, the low-mobility anions in the compositions of the invention are organic anions. Examples of organic anions are those derived from organic sulfate or sulfonates and may be alkyl, cycloalkyl, aryl, aralkyl or alkaryl sulfates and sulfonates. The anions useful in the invention may contain more than one anionic site, i.e., more than one ionizable group per molecule, for example, more than one sulfonic acid group per molecule. The sulfonates and sulfates useful as the low mobility anions in the compositions of the invention can be represented by formulas 1, 2, 3, 4, 5, 6 of the formula sheet.

In these formulas, RT is an aliphatic or an aliphatically substituted cycloaliphatic hydrocarbon or a hydrocarbon group, which is generally free from unsaturation and usually contains up to about 30 carbon atoms, although it may be polymeric and contain more than 30 carbon atoms. When R 'is aliphatic, it usually contains at least about 4 carbon atoms and when R' is alkyl-substituted cyeloaliphatic, the alkyl substituents preferably contain 1 to 4 carbon atoms. Specific examples of R 'are butyl, hexyl, octyl, lauryl, cetyl, octadecyl and groups, derived petroleum, saturated and unsaturated paraffin waxes and olefin polymers, including polymerized mono-olefins and diolefins containing 2 to 8 carbon atoms olefinic monomer unit. RT may also have other substituents, 8400207 - 13 - such as phenyl, cycloalkyl, hydroxy, mercapto, halogen, nitro, amino, lower alkoxy, lower alkyl mercapto, carbalkoxy, oxo or thio, or interfering groups such as -NH-, -0-, - S, but preferably their overall hydrocarbon character is retained.

2.

R is generally a hydrocarbon or an essentially hydrocarbon group having 1 to about 30 carbon atoms, although it may be polymeric and contain more than 30 carbon atoms. 2 R is preferably an aliphatic hydrocarbon group, such as 2 alkyl, alkenyl or alkylaryl. R may also have substituents, such as those mentioned above, including the aforementioned interfering groups, with the proviso that it is essentially hydrocarbon

N

the material character thereof is retained.

The group T in formulas 5 and 6 is a cyclic core, which may be derived from an aromatic hydrocarbon such as benzene or from a heterocyclic compound such as pyridine. Usually T is an aromatic hydrocarbon core and especially benzene. The caption and top caption x is the average number of ionized groups per molecule. The anion can contain additional sulfate or sulfonate groups, which are not ionized, but associated with some cationic species. In formulas 1 to 4, x can have a value up to 1000 or more,

1 O

when R is or polymer, but is preferably from 1 to 10, most preferably from 1 to 6, and generally the value is 1. The caption y in formulas 5 and 6 is a number ranging from 1 to 25 and is preferably 1.

Anionic compounds containing the anions represented by formulas I to 6 are highly available and can also be readily prepared by the known methods. Examples are salts with alkali or alkaline earth metals or ammonium salts.

Examples of sulfonates useful in the invention include the anions of the following acids: hexyl-9400207 if £ 14-sulfonic acid, octyl sulfonic acid, dodecyl sulfonic acid, octyl decyl sulfonic acid, lauryl sulfonic acid, mahogany sulfonic acid, paraffin wax sulfonic acid, benzenesulfonic acid, benzene sulfonic acid laurylcyclohexyl sulfonic acid, dodecyl benzene sulfonic acid; polyethylene sulfonic acids with 5 different molecular weights; polystyrene sulfonic acids of different molecular weights, etc. Styrene maleic anhydride copolymers bearing sulfonate groups on rings or styrene maleic anhydride copolymers partially or completely converted to the corresponding imide sulfonates are also useful anionic species in the invention; such materials are derived from styrene-maleic anhydride copolymers, typically with an inherent viscosity of about 0.06 to about 1, preferably about 0.06 to 0.3 dl g measured at 30 ° C in acetone, 0.4-1 g dl "1 .

A preferred embodiment comprises anions derived from aliphatic compounds containing two sulfonic acid groups and they can be represented by the formula 7 of the formula sheet, wherein n is an integer from about 2 to 20 or more, and preferably from about 2 to 12. These disulfonic acid salts can be prepared by known methods, for example, by the reaction of alkylene dihalides with sodium sulfite. Specific examples of such compounds include the salts of ethanedisulfonic acid, 1,4-butanedisulfonic acid, 1,5-pentanedisulfonic acid, 1,6-hexanedisulfonic acid, 1,8-octanedisulfonic acid and 1,10-25 decanedisulfonic acid.

Examples of sulfates that are useful include alkyl sulfates such as lauryl sulfates, and polyethylene sulfates of different molecular weights.

Another class of sulfates useful as the low-mobility anions in the compositions of the invention are polysulfated polyhydroxy compounds. Such compounds can be obtained by reacting polyhydroxy compounds with a suitable reagent such as fluorosulfonic acid to convert one or more of the hydroxy groups to sulfate groups. Examples of polyhydroxy compounds that can be used to prepare such poly-sulfates include pentaerythritol, mannitol, trimethylolpropane, dipentaerythritol, etc. As already noted, one or more of the hydroxyl groups in these polyhydroxy compounds can be sulfated to form of a variety of products. Ammonium sulfates can be prepared directly from polyhydroxy-10 compounds by reaction with an aminosulfonic acid in the presence of a diluent, such as dimethylformamide.

Amido, and preferably acrylamidoalkanesulfonic acid anions, can be used in compositions of the invention. These type examples of such anions are: 2,2-15 bisacrylamido-1,1-dimethylethanesulfonic anion; 2-acrylamido-2-methylpropanesulfonic anion; and poly (2-acrylamido-2-methylpropane sulfonic acid sodium salt of different molecular weights.

The low-mobility anions included in compositions of the invention can also be derived from pentavalent phosphorus compounds. Examples of such phosphorus compounds are phosphates, phosphonates and phosphinates.

The phosphorus compounds useful as the low mobility anions in the compositions of the invention can be represented by formulas 8, 9, 10, 11, 12, 13 and 14 3 11 of the formula sheet. R in these formulas is R or R yT, as defined above, or may be hydrogen, an alkali metal (e.g. lithium, sodium, potassium, etc.) or an alkaline earth metal 4 2 2 (e.g. calcium, magnesium, etc.). R is R or R yT, as defined above, or may be hydrogen, an alkali metal (eg, lithium, sodium, potassium, etc.), or an alkaline earth metal (eg, calcium, magnesium, etc.). Each of X, X, 3 X and X is oxygen or sulfur; and each a and b is 0 or 1. The 3400207 ** Zr-16 caption and top caption of z represents the average number of ionized groups per molecule. In formulas 11 to 14 1 9, z can be up to 1000 or more, when R or R4 is polymer, but is preferably from 1 to 10, most preferably from 1 to 4.5, and is generally I. It will therefore be appreciated that the pentavalent phosphorus compounds may be, for example, organophosphorus , phosphon or phosphine compounds, including the acids, alkali metal salts and alkaline earth metal salts thereof, or a thio analog of each.

Although effective electronically conductive compositions can be prepared by the method of the invention, which includes a polypyrrole or a copolymer of a pyrrole, and a little mobile anion as described above, the properties of the compositions can be improved by including other components that provide certain desirable properties. The electrolytic baths useful in the formation of the compositions of the invention will preferably contain a plasticizer. Plasticizers are known compounds which have the ability, when incorporated into polymeric compounds, such as polypyrrole or pyrrole copolymers, to increase elongation to stretch and / or to decrease polymer modulus and / or to increase flexibility. The latter criterion has been used to define the term plasticizer as the materials used in this application. Compounds which can increase the flexibility of the compositions of the invention are generally included in the electrolytic baths. In some instances, the low mobility anions included in the compositions of the invention have more than one function and may include, for example, the function of a plasticizer and / or a surfactant in the composition. For example, many of the higher molecular sulfates or sulfonates, mentioned above as low-mobility anions, can also act as plasticizers and, in addition, they can modify the wetting properties of the polymer . A specific example is sodium lauryl sulfate, which functions as a low-mobility anion and as a plasticizer for polypyrrole and copolymers of pyrrole.

The plasticizers useful in the present invention include organic sulfates or sulfonates such as alkyl, aryl, arylalkyl, alkaryl and polyolefin sulfates or sulfonates of the types previously mentioned as low mobility anions. Another class of compounds useful as a plasticizer in the compositions of the invention are polyhydroxy compounds.

The polyhydroxy compounds are preferably those containing 2 to 6 alcoholic radicals, at least one of which is unsubstituted. The unsubstituted polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, ara-bitol, adonitol, xylitol, mannitol, sorbitol, and neopentyl glycol.

Higher molecular weight polyhydric alcohols are also useful. Examples of such alcohols are various polyethylene glycols, and polypropylene glycol.

Partly acylated polyhydric alcohols can also be used. The partially acylated polyhydric alcohols are preferably those containing 2 to 6 alcoholic radicals, at least one, but not all of which are acylated with an aliphatic carboxylic acid having about 8 to about 30 carbon atoms. Examples include glycerol monooleate, glycerol di-stearate, sorbitan mono-stearate, sorbitan di-danooate, sorbitan tristearate, sorbitan dibehenate, erythritol mono-oleate, 1,1,1-trimethylpropane mono-myristate, pentaarytriltol diol oleol (9-riboleoleate), 9 , sorbitan monooleate, etc.

8 -: 0 0 2 0 7 ΪΓ r - 18 -

The polyhydric alcohols can also have ether bonds in the molecular structure. The ether-containing polyhydric alcohols can be obtained by dehydration of a polyhydric alcohol. Examples of such derivatives are sorbitan and mannitan. The ether-containing polyhydric alcohols can also be obtained by reacting a polyhydric alcohol with an epoxide. The epoxides are for the most part hydrocarbon epoxides and substantially hydrocarbon epoxides. The hydrocarbon epoxide can be an alkylene oxide or an aryl-alkylene oxide. Examples of the aryl alkylene oxides are styrene oxide, paraethyl styrene oxide and para chloro styrene oxide. The alkylene oxides mainly include the lower alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butene oxide and 1,2-hexene oxide. The substantially hydrocarbon epoxides can contain polar substituents. The polar substituent is usually a halogen radical, such as chlorine, fluorine, bromine or iodine; an ether radical such as methoxy or phenoxy; or an ester radical such as carbomethoxy. Examples of such epoxides are epichlorohydrin and butyl, 9,10-epoxy stearate. The number of ether bonds in the product is determined by the amount of epoxide added. It is thus possible to react polyhydric alcohol such as sorbitol with 1,2,3 or more equivalents of an epoxide such as propylene oxide.

The polyhydric alcohols for use in the present invention may also be ether-containing acylated polyhydric alcohols. These can be prepared by a number of methods. A polyhydric alcohol can be dehydrated and then acylated, or an alcoholic radical can be acylated first, followed by dehydration of other alcoholic radicals. As noted above, the ether bond can also be introduced by the reaction of an epoxide with the polyhydric alcohol before or after acylation. Examples of ether-containing 8400207-19 acylated polyhydric alcohols include polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene glycerol distearate, polyoxypropylene sorbitandiolino oleate and polyoxypropylene pentaerythritol monoooleate.

A particularly preferred example of a class of plasticizers that can be used in the compositions of the invention are polyalkylene polyols, polyethers and polyglycerols, and especially polyalkylene glyeols wherein the monomer unit I can contain up to about 4 carbon atoms and preferably about 2 carbon atoms. A specific example is polyethylene glycol. The molecular weight of the plasticizers can vary over a wide range depending on the composition to be modified and the properties to be modified by incorporating the plasticizer. Polyethylene-15 glycols of molecular weight from about 300 to about 5,000,000 are included in the electrolytic bath composition and are useful for modifying the properties of the compositions of the invention.

It has further been found that when the electropolymerization of pyrrole or polymerizable mixtures of pyrrole is performed using either a water medium or a multi-phase system as described below, the presence of polyethylene glycol over a range of molecular weights indicates mechanical strength and flexibility the polymeric compositions obtained. In addition, when polyethylene glycol of different molecular weights is added to electrolytic baths of the invention, the morphology of the obtained polymeric compositions can generally be modified by varying the molecular weight of the added glycol.

The amount of plasticizer included in the electrolytic bath of the invention can vary over a wide range, especially when the low-mobility anion 8400207 <-S '- 20 - also functions as a plasticizer. Generally, however, the electrolytic bath compositions of the invention will contain less than about 75% plasticizer, and preferably less than about 25% by weight plasticizer, based on the total weight of the bath composition.

The compositions useful in the preparation of the compositions of the invention may also contain redox species. Redox species are chemical species, which can undergo changes in the oxidation state and oxidize. 10 or can be reduced at an electrode. In this context, the species generally needs to be reduced before or during the reduction of the polymer beyond what is required to change the oxidation state of the polymer alone, and therefore stores additional charge. The oxidation and reduction of this species may or may not be reversible. The inclusion of redox species with suitable redox potentials in the compositions of the invention generally results in an increase in the loading capacity of the composition. The loading capacity of a polymer composition is the total charge consumed per 20 mass unit when the material is oxidized or reduced, usually expressed in cubic grams / g or ampere hours / kg. Examples of redox species which are effective include transition metal complexes and preferably anionic transition metal complexes. Examples of complexes include halide complexes, amine complexes, in which the amine may have the formula -NR ^ R ^ R ^, wherein each R ^, R ^ and R ^ can independently be a hydrogen or an alkyl or an aryl group; oxy complexes such as molybdates, tungstates, vanadates, cyanide complexes such as hexacyanide complexes of transition metals, iron cyanides, cobalt cyanides and molybdenum cyanide complexes. Other effective redox species include nitroprussides, polysulfides, transition metaloxy compounds, sulfur compounds or chalcogenides.

8400207 - 21 -

The redox species can be incorporated into the compositions of the invention in ionic form up to about 70% by weight based on the weight of the total composition.

Preferably, the redox species are included in anionic form 5 to the amount necessary to neutralize the charge on the polymer hull.

Surfactants, which are also referred to as wetting or emulsifying agents, may be included in the compositions of the invention and in the electrolytic baths used to form the compositions of the invention. The surfactant can be hydrophilic or hydrophobic. Typically, the surfactant is a hydrophilic surfactant and generally has an HLB (hydrophilic-lipophilic balance) in the range of about 10 to about 20.

The surfactant can be of the cationic, anionic, nonionic or amphoteric type. Many such surfactants of any type are known.

See, for example, McCutcheon's "Detergents and Emulsifiers", 1978, 20 North American Edition, published by McCutcheon's Division, MC Publishing Corporation, Glen Rock, New Jersey, USA, in particular pages 17-33, which should be considered incorporated herein .

Anionic surfactants contain negatively charged polar groups, while cationic surfactants contain positively charged polar groups. Amphoteric surfactants contain both types of polar groups in the same molecule. A general overview of effective surfactants is found in Kirk-Othmer 30 Encyclopedia of Chemical Technology, 2nd Edition, Volume 19, p.

507 et seq. (1969, John Wiley and Son, New York) and the aforementioned compilation, published under McCutcheon's name.

8400207 «'-I * · # * - 22 -

These publications are to be considered incorporated herein for their disclosure regarding cationic, amphoteric and anionic surfactants. Preference is given to the anionic or nonionic surfactants.

In addition, the low-mobility anion contained in the polymer can perform the function of a surfactant.

The effective anionic surfactant types include the known metal arboxylate soaps, organosulfates, sulfonates, sulfocarboxylic acids and their salts, and phosphates.

Effective cationic surfactants include nitrogen compounds such as amine oxides and known quaternary ammonium salts. Amphoteric surfactants include amino acid type materials and similar types. Various cationic, anionic and amphoteric dispersants are available industrially, especially from companies such as Rohm and

Haas and Union Carbide Corporation. Nonionic surfactants include alkylene oxide treated products such as ethylene oxide treated phenols, alcohols, esters, amines and amides. Ethylene oxide / propylene oxide block copolymers are also useful nonionic surfactants. Glycerol esters and sugar esters are also nonionic surfactants. A typical nonionic surface fictional agent class useful with the derivatives of the invention are the alkylene oxide treated alkyl phenols, such as the ethylene oxide treated alkyl phenol condensates, which are purchased by the Rohm and Haas Company. A specific example thereof is Triton X-100, which contains an average of 9-10 ethylene oxide units per molecule, has an HLB value of about 13.5, and a molecular weight of about 628. Many other suitable nonionic surfactants are known , see, for example, the aforementioned McCutcheon's as well as the dissertation "Non-ionic Surfactants", published by Martin J. Schick, M. Drekker Co., 8400207

a · V

W.

* * - 23 - i New York, 1967, which should be considered as inserted here.

Further information on anionic and cationic surfactants can also be found in the texts "Anionic Surfactants", Parts II and III, published by 5 W.M. Linfield, published by Marcel Dekker, Inc., New York, 1976 and "Cationic Surfactants", published by E. Jungermann,

Marcel Dekker, Inc., New York, 1976. Both publications are to be considered as incorporated herein.

The electronically conductive polypyrrole or eopolymers of pyrrole of the invention are prepared by electropolymerizing a pyrrole or copolymerizable mixture containing a pyrrole on an electronically conductive surface in an electrolytic bath. The electrolytic bath contains a pyrrole or a mixture of pyrrole and copolymerizable monomer, at least one electrolyte cell, which contains an anion which will be incorporated in the polymer during formation, and at least one liquid, in which the pyrrole (and / or copolymer) and electrolyte salt together have some limited solubility. The bath may additionally contain a second immiscible liquid or a gas or finely divided solid particles or combinations thereof. In one embodiment, the electrolytic bath contains a pyrrole or copolymerizable mixture of pyrrole and water. In another embodiment, the electrolytic bath contains the pyrrole or copolymerizable mixture of pyrrole and an organic diluent. In yet another embodiment, the electrolytic bath contains the pyrrole or copolymerizable mixture, which contains pyrrole, water and an immiscible liquid, but, for example, an organic diluent.

The last embodiment, in which the bath contains water and an immiscible organic diluent, hereinafter referred to as the two-phase system, is effective in the preparation of compositions of the invention, which can be characterized as porous and have a very large surface.

84 0020 7 # - 24 -

The electropolymerization of a pyrrole or a copolymerizable mixture containing a pyrrole using a two-phase system, such as water and an organic diluent, comprises the steps of A. immersing an electronically conductive surface in an electrolytic bath, which at least one liquid and at least one immiscible liquid, wherein the pyrrole or copolymerizable mixture is one of the liquids or is dissolved in at least one of the liquids and B. conducting an electric current through the bath at a voltage sufficient is for electropolymerizing the pyrrole or copolymerizable mixture containing a pyrrole on the electronically conductive surface. Preferably, one of the liquids is water and the immiscible liquid is an organic diluent. Examples of organic diluents useful in the present invention include organic hydrocarbons such as aliphatic or aromatic hydrocarbons, halogenated aliphatic or aromatic compounds, etc. Specific examples include white spirit, hexane, heptane, toluene, xylene, 1,2-dichloroethane , dichloromethane, carbon tetrachloride. and chlorobenzene.

The amount of the pyrrole or copolymerizable mixture containing pyrrole in the electrolytic bath can vary over a wide range, although the total amount is no greater. .

must then be the amount required to form the total amount of desired polymer. The amount of a pyrrole dissolved in the electrolyte solution component or electrolytic bath components should be sufficient to allow a reasonable reaction rate. This amount will usually range from about 10 molar to saturation of the electrolyte or electrolytes. The amount of electrolyte in the electrolytic bath should be sufficient to both conduct the desired current and provide sufficient anionic species for incorporation into the polymer for the purpose of charge neutralization. Typical concentrations are from 10 molar to saturation of the bath and especially 5 x 10 to 1 molar in at least one phase.

As noted above, the electrolytic bath of the invention may contain other ingredients which provide desirable properties to the compositions of the invention. For example, the bath may contain few mobile anions, plasticizers, redox couples, surfactants, etc., as defined above. When an aqueous system or a multi-phase system containing water is used for the electrolytic bath, an emulsifier or emulsion stabilizer can be included to stabilize this system.

The emulsifier can be an aliphatic glycol or a monaryl ether of an aliphatic glycol. The aliphatic glycol can be a polyalkylene glycol. It is preferably a glycol, wherein the alkylene radical is a lower alkylene radical of 1 to 10 carbon atoms. The aliphatic glycol is exemplified by ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, tetramethyl clay glycol, hexamethylene glycol, and the like. Specific examples of the ethers are monophenyl ether of ethylene glycol, mono (heptylphenyl) ether of triethylene glycol, mono (α-octyl-B-25 naphthyl) ether of tetrapropylene glycol, mono (polyisobutylene (molecular weight 1000) -substituted phenyl) ether of octapropylene glycol and mono (o, p-dibutylphenyl) ether of polybutylene glycol, mono (heptylphenyl) ether of trimethylene glycol and mono (3,5-di-octylphenyl) ether of tetra-trimethylene glycol, etc. The monoaryl Ethers are obtained by condensing a phenolic compound such as an alkylated phenol or naphthol with one or more moles of an epoxide, such as ethylene oxide, propylene oxide, triethylene oxide or 2,3-hexylene oxide. Condensation is promoted by a basic catalyst, such as an alkali or alkaline earth metal hydroxide, alcoholate or phenate. The temperature at which the condensation is conducted can be varied in a wide range, such as from room temperature to about 250 ° C. Preferably 50-150 ° C are preferred. More than 1 mole of the epoxide can condense with the phenolic compound, so that in the molecular structure the product may contain one or more of the radicals derived from the epoxide. A polar substituted alkylene oxide, such as epichlorohydrin or epibromohydrin, is also effective for preparing the monoaryl ether product, and such product is also effective as an emulsifier.

Also useful as an emulsifier are the mono- or di-alkyl ethers of the aliphatic glycols, wherein the alkyl radical preferably has 2 to 20 carbon atoms (eg octyl, nonyl, dodecyl, behenyl, etc.). The fatty acid esters of the monoaryl or monoalkyl ethers of aliphatic glycols are also useful. The acids include, for example, acetic acid, formic acid, butanoic acid, hexanoic acid, oleic acid, stearic acid, behenic acid, decanoic acid, iso-stearic acid, linolenic acid, as well as commercial acid mixtures as obtained by the hydrolysis of tall oils, sperm oils, etc. Specific examples are the oleate of mono- (heptyl-phenyl) ether of tetraethylene glycol and the acetate of mono- (polypropylene (molecular weight 1000) -substituted phenyl) ether of tri-propylene glycol.

The alkali metal and ammonium salts of sulfonic acids are also emulsion stabilizers. The acids are illustrated by decyl benzene sulfonic acid, di-dodecyl benzene sulfonic acid, mahogane sulfonic acid, heptyl benzene sulfonic acid, polyisobutylene sulfonic acid (molecular weight 750) and decyl naphthalene sulfonic acid and tri-decyl benzene sulfonic acid. The salts are illustrated by the sodium, potassium or ammonium salts of the above acids.

m 8400207 '. · * »* .- 27 -

Emulsifiers include phosphatides, especially those of the formula 15 of the formula sheet, wherein G is selected from the group consisting of fatty acid acyl radicals and phosphorus-containing radicals having the structural group 16 of the formula sheet, wherein R 'is a lower alkylene radical having Is 1 to about 10 carbon atoms and R 1 and R 1, f are lower alkyl radicals of 1 to 4 carbon atoms and at least one, but no more than two of the G radicals are the phosphorus-containing radicals. The fatty acid acyl radicals are, for the most part those derived from the 10 fatty acids having 8 to 30 carbon atoms in the fatty acid radicals such as octanoic acid, stearic acid, oleic acid, palmitylic acid, behenic acid, myristic acid and oleostearic acid Particularly desirable radicals are those derived from commercial fatty acid compounds such as soybean oil, cottonseed oil and ricin seed oil. particularly effective phosphatide is soybean lecithin, which is described in detail in Encyclopedia of Chemical Tec hnology, Kirk and Othmer, volume 8, pp. 309-326 (1952).

As additional emulsion stabilizers, the neutral alkali metal salts of the fatty acids having at least 12 aliphatic carbon atoms in the fatty acid radical can also be used.

These fatty acids mainly include lauric acid, stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, linolenic acid, behenic acid or a mixture of such acids as obtained from hydrolysis of tall oil, sperm oil and other commercial fats.

Only a small amount of a stabilizer is needed for the purpose. It can be as low as 0.01 parts and is rarely more than 2 parts per 100 parts by weight of the electrolytic bath.

In the majority of cases, the amount in the range is from 0.1 to 3 parts per 100 parts of the bath.

As noted above, the electropolymerization process used in the invention may be carried out in an organic diluent and more particularly in an organic phase, which is less than about 3% and preferably less than about 1 % water. Examples of organic connecting agents are polyols, organic carbonates, ethers, nitriles, etc. It is essential that the solvent does not contain any cont. undergoes curative oxidation during electropolymerization and thus interferes with polymerization or significantly reduces the flow efficiency of the polymerization process. ,

However, a preferred embodiment of the invention is the electropolymerization of aqueous media pyrrole, either a single phase aqueous system or a multiphase aqueous system. Many of the advantages of using aqueous systems are evident, including lower cost, availability and easy purification of water, the ability to use a wide range of ionic materials as electrolyte salts in water, the ability to add high concentrations adaptation of ionic species, allowing for high electrochemical currents and high polymer flow rates. Under controlled conditions, intact homogeneous films of polypyrroles 20 can be formed on a variety of substrates in aqueous media. Thickness ranges from less than 100 Angstroms to a few millimeters for denser materials. In some cases, the current density affects the morphology. The morphology of the electro-polymerized compositions of the invention can be further modified using the additives already discussed.

It has been found that improved results are obtained when the electroplating bath is stirred vigorously during the electropolymerization of the monomers. Stirring may be by any known method, including vigorous stirring with paddle mixers, magnetic stirrers, ultrasonic devices, vibration, or by puncturing gases through the bath to provide sufficient movement (including gases formed on the counter electrode). Electropolymerization takes place by passing an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or copolymerizable mixture containing a pyrrole and an electronically conductive surface immersed in the electrolytic bath. The electric current can be a continuous electric current or a varying electric current, such as a pulse current. In addition, the electric current is direct current, although alternating current may be effective in some instances.

The voltage at the anode should be sufficient to oxidize the monomer without causing significant changes in the bath, such as degradation of a bath component, which could adversely affect polymerization. Generally, current densities of up to 2 amperes per cm can be used, but preferably current densities greater than 500 mAmp. o per cm, applied. In more preferred embodiments, the current density will be less than 250 and more generally, less than 100 milliAmp. per cm.

At the aforementioned current densities, the pyrrole or copolymerizable mixture of a pyrrole is electro-polymerized at the electronically conductive surface. Depending on the specific ingredients in the plating bath, the electropolymerizable polypyrrole may either be formed as a powder at the electronically conductive surface and fall and dispersed in the electrolytic bath and, on the other hand, be deposited on the conductive surface. The deposit can be in the form of a film, which is either smooth and dense or irregular with less than the bulk or theoretical density. Bulk of theoretical density of the polymers is the density of continuous, pure polymer, which does not contain voids, pores, voids or inclusions. The bulk or theoretical density can simply be determined according to flotation methods 8400207 t, w - - 30 -. Examples of irregular transfers include porous films, powders, dendri-form materials, etc. The nature of the cation or cations as well as the anion or anions present in the electrolytic bath affects the electropolymerization. The morphology of the deposition on the electronically conductive substrate can be checked and modified by incorporating in the electrolytic bath various complexing agents for the ionic components of the electrolyte. The examples of the materials which function as growth regulators when incorporated into the electrolytic bath include the aforementioned nonionic plasticizers (eg, polyalkylene glycol such as polyethylene glycol), crypt teeth, and commercially available crown ethers such as 12-Crown-4, 15-Crown-5 , and 18-Crown-6, which are available from Aldrich 15 Chemical Co ..

The temperature of the electrolytic bath during the electropolymerization process is generally kept between about 15 to about 50 ° C, although polymerization proceeds over a much wider temperature range. The reaction is carried out at about room temperature and preferably under thermostatic conditions.

A variety of electronically conductive substrates that do not undergo competitive oxidation during the electropolymerization can be used in the method of the invention. Not all types of metals can be used with the entire range of bath compositions. For example, although steel surfaces are effective for electropolymerizing pyrrole in the presence of sodium lauryl sulfate and water, the electrolytic bath, containing pentaerythritol tetrasulfate and water, will not deposit a satisfactory film on steel, but will deposit a satisfactory coating on nickel substrates. The selection of a particular substrate material can be easily determined by those skilled in the art, with minimal experimentation.

The size and shape of the substrate used in the method of the invention will vary depending on the type of cell in which the electropolymerization process is carried out and on the desired shape of the polymer. For example, when flat films are desired, the substrate will be in the form of a flat panel in a parallel plate cell.

A preferred embodiment of the invention includes a rotary cylindrical anode and a moving tape electrode from which the polymer is removed in a continuous process. The polymer can also be collected or stripped continuously from a stationary electrode.

. The time required to form a certain amount or thickness of polymer will depend on several factors, including the flow density, bath temperature, the size or physical dimensions of the electronically conductive surface, and the temperature of the electrolytic bath. In addition, the specific type of the desired morphology will be an important consideration when choosing the values of the process variants, such as temperature, current density, coating time, voltage, etc.

One of the examples of the method according to the invention, in particular with the water systems according to the invention, is the ability to form films with controlled thickness or a large range of thicknesses and in particular films with thicknesses greater than 250 µm, and in particular thicknesses between a range of 0.5 mm to 2 cm. Many known processes have not been developed to the level required for anything other than thin films (200 µm or less).

In the general process of the invention, the electronically conductive surfaces are introduced into the electrolytic bath and connected to a power source. The polymer is formed 8400207 i -32- at the anode. The counter electrode may consist of the bath-y-fl tank or a separate conductive surface or surfaces may be placed in the electrolytic bath. The bath may have a separate compartment for the secondary electrode, but the one compartment configuration is preferred.

* I

When the electropolymerization process is completed, the substrate is removed from the electrolytic bath and the electropolymerized material is mechanically removed from the surface. This polymer can be washed with water and various non-aqueous solvents (eg ethers, liquid hydrocarbons, etc.) to remove any unwanted deposits present on or in the material.

i

If the deposited material is not completely dried, it can be accomplished, if desired, by heating the polymer at a higher temperature, preferably under vacuum. The temperatures selected will depend on the nature of the pyrrole or copolymerizable mixture of pyrroles used in the process, but will generally be less than 250 ° C and preferably less than 100 ° C.

*

As noted above, the morphology and physical nature of the compositions electro-polymerized according to the method of the invention will depend on a number of factors, including the nature of the substrate, the solvent, the temperature, the agitation, the current density, the electric potential, etc. Continuous films having a density approximately equal to the bulk density of the polymer can be prepared by the process of the invention when single-phase organic or aqueous systems are used. When more irregular films characterized by low density and large surface area are desired, the multi-phase processes described above are in particular the two-phase phase. Aqueous Systems, Advantageous In one of the preferred embodiments, the low-mobility anions are incorporated into the compositions of the invention by incorporating these anions into the electrolytic baths. When incorporated into the polymeric compositions of the invention, the anions, as noted above, have low motility and are permanently retained in the polymer upon reduction and on all subsequent oxidations or reductions.

One of the unexpected advantages of preparing the pyrrole polymers and copolymers of the invention, which contain the low-mobility anions, is the fact that the polymer is capable of being discharged and recharged for at least hundreds of cycles. See, for example, Example 21. This is surprising because it is expected that highly mobile anions will give the greatest reversibility. The mechanism for the observed reversibility is not known, but it is believed to include forced transport by another ion or ions. Such compositions are therefore classified as being electrochemically reversible polymers and are therefore effective in the preparation of?

The following examples illustrate the method of the invention. Unless otherwise stated, all parts and percentages are parts by weight and percentages by weight.

Unless otherwise noted, in the following examples, electropolymerizations are performed at 2 amperes for 30 minutes using a Hanovia arc lamp power supply, checked with a Variac. Stirring takes place with a horizontally perforated glass disc mounted on the bottom of a stir bar (approximately 1 to 2 cm from the bottom of the bath) and quickly vibrated up and down with a Vibro mixer (Model El , supplied by AH Fur Chemie-Apparatebau Mannedorf-Zurich). The temperature is controlled with an ice bath.

8400207 ^ * »- 34 -

Both electrodes are 15 x 7.5 x 0.05 cm panels of steel (AISI

No. 10/10) in parallel plate configuration, which are stiffened with toluene. The surface (one side) of each electrode, which is in it. . 2 bath is immersed, is 70 cm and the distance between the electrodes 5 is 5.5 cm. The polyethylene glycol used in some of the examples has an average molecular weight of about 15-20000. The bath is exposed to atmosphere. The descriptions of the polymer films in the following examples do not include the edge effects. These effects cause irregularities, which rarely exceed 5% of the total mass of the. cover film.

Example I

In this example, the following components were used: grams

Pyrrol 40

Sodium lauryl sulfate 40 20 Polyethylene glycol 20

Distilled water 1600

Heptane 2000 (ml)

The first four ingredients were mixed into a homogeneous mixture in a vessel and 375 ml of this mixture was added to the reaction vessel of dimensions 10.8 x 8.9 x 5.7 cm. Two steel panel electrodes are put in place.

Heptane (50 ml) is added and stirring is performed mechanically with a Vibromixer.

30 Four films are manufactured separately at 2

amperes using a reaction time of 30 minutes. The temperature is controlled in an ice bath and is initially 21 ° C

8400207 * * - 35 - and rises to about 34-37 ° C during the reaction. The current is kept at 2 amperes, but the voltage changes from about 60 to about 40 Volts during the reaction. The electrolyte side of each film has irregularities in the form of dendriform protrusions (about 1 millimeter) and these protrusions are removed by light sanding by removing the films from the electrode surfaces. Each film is rinsed well in distilled water and in heptane.

Two of the films are completely dried in a vacuum oven for 24 hours at 50 ° C. The films cleaned in this way are found to contain three layers. The first layer, which is the layer closest to the steel panel, is smooth and continuous.

The second layer, adjacent to the smooth layer, is a uniformly porous material and the third layer, adjacent to the second layer, is denser and more porous than the second layer. The other two films obtained in this example are stripped from their backing or smooth layer and cut into 0.19 cm strips. The strips are cleaned in a Soxhlet extractor for 15 hours with distilled water. After drying at room temperature, the pieces are further dried in a vacuum oven for 24 hours at 50 ° C.

Example II

A mixture of 5 g of pyrrole, 1 g of sodium ethane disulphonate, 2 g of polyethylene glycol and 200 g of water is prepared and added to a reaction vessel measuring 8 x 7 x 4.5 cm. The cathode is a 15 x 5 x 0.025 cm piece of Precision brand steel (a Precision product identified as NIDA / SIDA 1613 D Al). The anode 30 is a Nickel 200 panel with dimensions 10 x 5 x 0.05 cm (Nickel 200 is a product of Inco, identified as a very pure nickel). The surface (one side) of each electrode, dipped 8400207 *> «* - 36 - 2 in the bath, is approximately 40 cm. Toluene (20 ml) is added and the mixture is stirred with a Vibro mixer. The electro-polymerization reaction takes place for 15 minutes at a constant current of 0.5 amperes at a potential of about 17 Volts. The film formed around the electrode is removed and appears to be a relatively porous uniform film 0.3 to 0.4 mm thick.

Example III

10

A mixture of 200 g of pyrrole, 4 g of pentaerythritol tetra hydrogen sulfate, 4 g of polyethylene glycol and 800 g of water is prepared and mixed homogeneously. A volume of 375 ml is added to a 5.7 x 8.9, 10.8 cm reaction vessel and 50 ml of dichloromethane are also added to the vessel. In this example, a steel panel (AISI No. 10/10) (15 x 7.5 x 0.05 cm) is used as the cathode and a Nickel 200 sheet (14.2 x 7.6 x 0.025 cm) is used as the anode. The electropolymerization normally takes place over a period of 15 minutes, maintaining a current of 2 amperes. A porous mass with a thickness of about 1 cm and a lower density (less than 0.1 g / cm) is obtained; this porous mass is electronically conductive.

25 Preliminary IV

A mixture of 200 g of pyrrole, 10 g of sodium 1,10-decane disulfonate, 10 g of polyethylene glycol and 800 parts of water is prepared and 375 ml is added to each of two reaction vessels. Heptane (50 ml) is added to each reaction vessel and the electropolymerization is normally carried out at a flow of 2 amperes. The electropolymerization of the first reaction vessel 8400207 - «*

It is stopped after 5 minutes to obtain a thick black electronically conductive film covered with small dendri-shaped protrusions about 1 mm in height.

The electropolymerization reaction in the second vessel 5 takes place for 39 minutes to obtain a thicker base film covered with small dendri-shaped protrusions of approximately the same dimensions as in the previous film.

Example V

10

A mixture of 10 g of pyrrole, 10 g of sodium lauryl sulfate and 0.5 g of polyethylene glycol is prepared and added to the reaction vessel. In this example, both electrodes are steel panels and the stirring takes place with a Vibromen mixer. The electropolymerization reaction is carried out for 20 minutes at a current of 2 amperes. A thick, fairly uniform coating is deposited on the anode, and the coating is covered with small dendri-shaped protrusions, which are easily removed by light rubbing.

20

Example VI

The procedure of Example V is repeated, except that 50 ml of heptane are added to the mixture in the reaction vessel and the electropolymerization takes place at 2 amperes for 5 minutes. The film produced in this way is more porous than the material obtained by the method of Example V and is covered with dendri-shaped projections.

Example VII

Pentaerythritol ether sulfate ammonium salt is prepared 8400207 * - - 38 - from pentaerythritol and sulfamic acid in Ν, Ν-dimethylformamide. A mixture of 5 g of pyrrole and 5 g of the ammonium salt in 200 ml of water is prepared and electro-polymerized in a reaction vessel measuring 8 x 7 x 4.5 cm, in which the cathode is a Precision steel sheet measuring 5 x 5 c 0.025 cm and the anode is a 6.4 x 5 x 0.025 cm 2 nickel sheet. About 20 cm of the nickel sheet are dipped in the bath. The distance between electrodes is 4.5 cm. Electropolymerization takes place at a current of 0.3 amperes for 10 minutes to yield a black electronically conductive film which has been cracked by a slightly rough surface on the dissolution side of the film.

Example VIII

The procedure of Example VII is repeated, except that 2 g of polyethylene glycol is included in the mixture contained in the reaction vessel. The black electronically conductive film thus obtained is more uniform and smoother on the dissolution side than the film obtained in Example 20 VII.

Example IX

Mannityl hexasulfate ammonium salt is prepared from a mannitol and sulfamic acid in dimethylformamide. A mixture of 5 g of pyrrole and 1 g of this ammonium salt is dissolved in 200 ml of water. In the device described in Example VII, the electropolymerization is carried out at a current of about 0.4 amperes for 20 minutes. The product is a black electronically conductive film, which is glossy on the substrate side and rough on the solution side.

8400207 • * - 39 - * ·

Example X.

The procedure of Example IX is repeated, except that 2 g of polyethylene glycol are added to the mixture in the reaction vessel. In this example, a more uniform film is obtained, which is smoother on the solution side.

Example XI

A mixture of 15 g of pyrrole and 500 g of water is prepared and a second mixture of 10 potassium ferricyanide and 5 g of polyethylene glycol in 400 ml of water is prepared. The two solutions are mixed and shaken. About 450 ml of the mixture is poured into a 10.8 x 8.9 x 5.7 cm reaction vessel. The electrodes used in this example are both steel panels.

The electropolymerization takes place at 5 amperes. At the start of the reaction, the temperature is 23 ° C and the voltage is 22 volts.

During the electropolymerization reaction, the temperature is stabilized with an ice bath at 31-32 ° C. At this temperature 20 volts is required to maintain a current of 5 amperes. The distance between the electrodes is 5.5 cm. The electropolymerization reaction is carried out for 40 minutes. The polymer is then removed from the anode. The film is 0.8 mm thick, black and electronically conductive. The film is smooth on both sides, although smoother on the substrate side.

Example XII

The procedure of Example XI is repeated except that the 15,000-20,000 molecular weight polyethylene glycol is replaced by an equivalent weight Carbowax 4000 (a product of Union Carbide identified as a poly-8400207 '4' Λ -40-ethylene glycol with molecular weight 4000). The electropolymerization reaction is run at a current of 5 amperes and about 20 volts are required to maintain this current during the reaction period of 40 minutes. The temperature of the bath varies from 21 to 32 ° C. The polymer is removed from the electrode and film obtained in this way is black and electronically conductive. The substrate side is smooth, while the solution side is covered with dendri-shaped structures.

Example XIII

A mixture of 2 g of pyrrole, 0.4 g of a 50% aqueous solution of the sodium salt of 2-acrylamino-2-methylpropanesulfonic acid and 100 ml of water is prepared and mixed homogeneously.

In this example, the cathode of the reaction vessel is a platinum strip (0.5 x 3 cm) and the anode is a gold surface (2x4 cm) 2 of which 4 cm are immersed in the bath. The electrodes are rinsed with distilled water before use. The electropolymerization in this example is performed using a Hewlett Packard power supply / amplifier model 6824A. The electro-polymerization reaction is carried out at a current of 24 milli-amperes and a voltage of 15 volts over a period of 2 minutes. A thin black electronically conductive film is deposited on the gold surface, 25

Pre-XIV

The procedure of Example XIII is repeated, except that the electrolyte salt used is poly (2-acrylic-30-amido-2-methylpropanesulfonic acid sodium salt with an inherent viscosity of 0.1 parts g * (measured in 0.5N NaCl at 30 ° C) The electropolymerization takes place at 30 milliamps at 20 volts for 2 minutes and a smooth thin glossy black electronically conductive film is deposited on the gold surface.

Example XV 5

A mixture of 20 g of pyrrole, 20 g of sodium lauryl sulfate, 10 g of polyethylene glycol and 800 g of water is prepared and 375 ml of this mixture is added to the 10.8 x 8.9 x 5.7 cm reaction vessel. Heptane (50 ml for each run) is then added to the reaction vessel and stirring is performed with a rapidly vibrating glass disk. The temperature is controlled with an ice bath. In this example, the electropolymerization takes place with a current of 2 amperes. The reaction time is 30 minutes and the reaction temperature ranges from 20-38 ° C. The polymer formed on the anode is removed and purified by washing several times in distilled water. The film prepared in this manner contains a very thin base layer adjacent to the substrate, a uniform porous layer adjacent to the base layer and a denser wrinkled less porous layer on the electrolyte side. The polymer layer is removed from the electrode and 4 x 1 cm strip is cut from the film and its thin base layer is removed. The rest of the film is broken into pieces and rinsed several times along the strip with distilled water. The pieces and strip are then further rinsed in a Soxhlet extractor using distilled water for 15 hours (about 40 extractions). The materials are then dried in a vacuum oven at 80 ° C for 29 hours. This polymer is electronically conductive and can be ground to a porous powder which can be easily pressed into various desired shapes without additives. The shapes obtained in this way are also electronically conductive.

8400207 + ft · »- 42 -

Example XVI

The procedure of Example XV is repeated, except that the mixture contains only 7.5 g of polyethylene glycol 5. The electropolymerization of the mixture results in a thinner, denser film than is obtained in Example XV. The film also appears not to be as flexible and the corresponding powder cannot be pressed as well as the powder obtained in Example XV.

10

Example XVII

The procedure of Example XV is repeated, except that the mixture contains only 5 g of polyethylene glycol. The film obtained in this way is electronically conductive, is thinner than the film obtained in Example XVI and is less uniform.

PREVIOUS XVIII

20

A mixture of 40 g of pyrrole, 40 g of sodium lauryl sulfate, 15 g of polyethylene glycol and 1600 g of water is stirred until the mixture is homogeneous and 1200 ml are added to a 8.25 x 14 x 19 cm plastic reaction vessel. Both electrodes are 25 14 x 19 x 0.1 cm panels of steel (AISI No. 10/10) plate, which has been degreased with toluene. Heptane (150 ml) is added and stirring is done with a Vibromixer. The surface of the 2 anode, covered with polymer, is about 250 cm. The electropolymerization reaction takes place for 1 hour at a current of about 4 milliamperes DC. The product is removed from the anode and partly powdered by hand, washing with distilled water. After further washing (Soxhlet 8400207-43 - extraction with distilled water) and drying (vacuum oven, 35 ° C, 20 hours), the polymer was further powdered in a mortar. In this way, a fine black electronically conductive powder is obtained.

The powder obtained in this example can be tested cold in the dry state at room temperature, without any additives, and the pressed electrodes obtained in this way have an improved electronic conductivity, compared to the dried electropolymerized films. The density of the -3 electro-polymerized film is about 0.2 g.cm, while the -3

density of the pressed electrode is about 0.8 g.cm. Example XIX

The procedure of Example XVIII is repeated except that the energy source is a simple 12 ampere whole wave rectifier controlled by a Variac. The voltage requirements are identical to those of Example XVIII.

Example XX

An electrolyte bath is prepared containing 1 g of phenylsulfonic acid and 2 g of pyrrole in 100 g of water. The electropolymerization takes place in the undisturbed bath on a gold strip measuring 3 x 0.5 cm. The gold strip is immersed to a depth of 1 cm. A platinum counter electrode is used, and a current of 1 milliamp is maintained for 300 seconds. The product is a black electronically conductive film.

In particularly advantageous embodiments, polymers or copolymers according to the invention can be heat treated to increase the electrochemical storage capacity. Heat treatment preferably takes place at a temperature above the transition temperature of the composition observed during differential scanning calorimetry (DSC) in the range of about 60 ° C. A temperature in the range of about 60 to the decomposition temperature of a polymer, preferably about 80 to about 100 ° C, for example, can be used. Heat treatment preferably takes place under a vacuum or partial vacuum (for example, a pressure of about 1 mm Hg absolute or less) and continues until equilibrium is reached or nearly reached (for example, about 10 to about 20 hours).

The electronically conductive polymers or copolymers prepared according to the invention are useful, for example, for electrodes in electrochemical cells (for example, as electrodes in batteries, both primary and secondary batteries); 15 as photocell coatings to prevent photocorrosion or corrosion processes; for catalytic electrodes, for electrical conductors; for conductive substrates and / or binders and composite electrode mixes; for switchgear; and as durable or corrosion resistant electropolymerized coatings. The electronically conductive polymers of the invention are also useful in solid state applications (e.g., in the formation of compounds) and / or for photovoltaic and photoelectrochemical devices, and as reversible electrodematerials in electrochemical cells and batteries.

Electrodes made according to the invention may be positive or negative and may contain, in addition to polymer, a suitable binder material and / or suitable high surface area carbon material. They can also contain at least one other redox species. Suitable binder materials are inert polymeric binders that do not interfere with the electrochemical behavior of the electrons obtained. An example of such a binder material is a halogenated polymer material, such as 8400207, polytetrafluoroethylene, which is preferably introduced from an aqueous suspension, which suspension is commercially available, for example, from DuPont under the trade name Teflon T30B. Polytetrafluoroethylene, introduced in the form of a powder, can be used. Other polymers, for example polypropylene, may be suitable for use and such compositions under conditions which are not highly oxidizing. Suitable high surface area cabbage are those materials having surfaces from about 1 to about 2000 m per gram, preferably about 16 to about 1200 m per gram. Examples of commercially available high surface area carbons which are useful are RB Carbon, which has an area of about 1200 m 2 per gram and Shawmigan Black, which has an area of about 60 to about 65 m per gram.

Polymeric electrodes can be made according to the invention by mixing a polymer according to the invention together with the optional ingredients of binder, high surface area carbon and / or other redox species with water or an organic liquid (eg lab petrol) to provide a pasty mixture. The pasty mixture can then be cold pressed or rolled by standard methods, preferably at a pressure in the range of from about 2 to about 840 kg / cm and a pressure in the range from about room temperature to the decomposition temperature of the polymer, for providing an electrode of a desired shape. The polymer is preferably heat-treated to increase the electrochemical storage capacity before or after incorporation into the mixture.

The polymeric electrodes obtained according to the invention, either as anodic films or pressed from powders, are suitable for use in electrochemical cells, in particular electrochemical storage cells or batteries (both 8400207 t 4

B

- 46 - maire as secondary batteries) as the positive and / or negative electrode. These electrodes can be of any size and shape, such as a size and shape depending on the size and shape of the electrochemical cell or battery for which they are used.

In electrochemical cells, in which the polymeric material of the invention is the positive electrode, a negative metal electrode can be used. The negative metal electrode is designed and manufactured according to standard methods and is preferably an alkali metal or an alkaline earth metal or an alloy thereof. Preferred alkali metals are lithium, sodium and potassium. Preferred alkaline earth metals are magnesium and calcium. Suitable alloy materials are, for example, aluminum and silicon.

In electrochemical cells, in which the polymeric material of the invention is the negative electrode, the positive electrode can be made of any material (ie, metal or non-metal) provided that such a positive electrode is electrochemically more positive than the polymeric negative one. electrode according to the invention.

Both polymeric positive and negative electrodes can be provided in an electrochemical cell of the invention. These electrodes can have different compositions or can have the same composition and / or be manufactured by the same method, provided that such electrodes can be sufficiently adapted to different charge states to provide an effective electrochemical cell. The polymeric electrode (negative and positive) provided according to the invention preferably contain porous electronically conductive compositions containing an electropolymerized polypyrrole or pyrrole copolymer with an apparent density. -3 to about the bulk density of the 8400207-47 polypyrrole or copolymer and a surface area of at least twice the surface area of a bulk density smooth film of this composition. These electrodes preferably contain one or more less mobile anions, characterized by an average ionic transport number during reduction less than about 0.1, preferably less than about 0.01. An advantage of the positive electrodes containing the polymers provided in accordance with the invention is that the electronic resistance of such electrons increases as the cell discharge voltage approaches 0 volts 10, thereby protecting the electrochemical cell from damage due to over-voltage. discharge.

In the drawing, figure 1 is a laboratory scale lithium cell with a large outer vessel 1 with a lid 2. The lid 2 has a hole in the center in which a rubber stopper is arranged. In the large vessel 1 is a small vessel 2, which is held in place by a rubber flange 14. The elements of the lithium cell are contained in the small container 4. The larger container 1, the lid and the plug 3 are used to maintain a certain atmosphere, such as argon. The desired atmosphere, for example argon, is introduced through plastic tubes through the plug as shown at 10 and the argon is discharged through the tube 11. A strip 6 of the polymer according to the invention is suspended in the inner container 4 by means of nickel contacts 13 and two lithium electrodes 5 and 9 are also suspended by the plug 3 in the inner container 4 by means of platinum hooks 8. The polymer electrode 6 is a positive electrode, while the lithium electrode 5 is a negative working electrode and the lithium electrode 9 is a referential electrode. The working electrode 5 is larger than the reference electrode 9. Sufficiently non-aqueous electrolyte 12 is added to the interior of the container 4 to provide an electrolyte level 15 below the platinum hooks 8 and to cover part of the positive electrode 6 and the 8400207 m * t - 48 - two lithium electrodes 5 and 9.

The reversible storage of charge in the materials of the invention is also demonstrated in a cell in an argon-filled box, Figure 2. The glass container 30 contains 50 ml of non-aqueous electrolyte 31. A strip 32 of a polymer of the invention holds between strips 33 and 34 of active lithium metal and is in electrochemical ionic contact with strips 33 and 34 by means of the electrolyte 31. The lithium electrode 33 is a negative electrode and acts as a source (during discharge) 10 and a well (while charging) lithium ions. The lithography electrode 34 is placed close to the strip 32 and serves as a reference electrode; no current flows through the electrode 34.

When active metals such as lithium, sodium or calcium are used as negative electrodes, non-gaseous electrolytes are used. Typically these electrolytes are organic liquids, which have salts of the electroactive species dissolved therein. For example, in the case of cells using negative lithium electrodes, known electrolytes are used such as propylene carbonate / 1.0M lithium perchlorate (PC / 20 1.0M lithium chlorate), tetrahydrofuran / 1.5M lithium hexafluoroarsenate, 2Me-tetrahydrofuran / 1.0M lithium hexafluoroarsenate, mixtures thereof, etc.

The invention also includes primary and secondary batteries, Figures 3 and 4, which contain the 45 negative alkali metal electrodes (eg, lithium, sodium, or potassium); the schelder 46; polymeric positive electrode 47 made in accordance with the invention; ceramic or glass feedthrough insulator 49; spacers 50 and 51; and the negative metal electrode contact 52. The metal housing 48 provides the holder for the cell components 30 and electrical contact to the positive electrode 47. The negative electrode 45 is electronically isolated from the positive electrode contact 48 by the insulator 49. Alternatively, the cell holder 8400207 * are provided by an insulating material, such as plastic, and electrical contact can be made through the electrodes by means of metallic grids, screens, foils, etc. In a preferred embodiment, a cylindrical winding of the negative electrode 45, separator 46, and positive electrode 47 in a cell with a spiral configuration.

Another preferred embodiment of the invention, Figure 5, is a laboratory scale electrochemical energy storage cell 60 which has a layered configuration and includes the positive polymer electrode 61 made in accordance with the invention, negative lithium electrode 62, the lithium reference -electrode 63, glass fiber separators 64, gold contacts 65, 66 and 67, glass plates 68 and 69 and an epoxy seal 70.

The cell is assembled in dry air or in an inert atmosphere, for example argon.

Another preferred embodiment of the invention includes the layered or stacked cell 61 (Figure 6), in which a plurality of positive and negative electrodes are respectively connected in parallel to increase the maximum current that can be provided by the resulting battery pack. The cell 71 includes parallel placed polymeric electrodes 72a-d provided in accordance with the invention and parallel placed negative electrodes 73a-d parallel to and spaced from the electrodes 72a-d. The electrodes 72 and 73 are arranged in the holder 74. The holder 74 is preferably electronically insulating. The electrode 73a is spaced parallel between electrodes 72a and 72b. The electrode 73b is spaced parallel between the electrodes 72b and 72c. The electrode 73c is spaced parallel between the electrodes 72c and 72d. The electrode 73d is spaced parallel to the electrode 72d. The electrodes 72a-d are connected to the contact 76, which protrudes from the holder 74. Likewise, the electrodes 73a-d are connected to the contact 77, which protrudes from the holder 74. The separator material 75, which contains a suitable electrolyte, is dispersed through the interior of the container 74. Although four electrodes 72a-d and four electrodes 73a-d are shown in the illustrated embodiment, it will be understood that the number of such electrodes can be smaller or larger than four, which number depends on the requirements for the cell 71.

In yet another embodiment of the invention, the layered or stacked cell 81 (Figure 7) is provided, wherein a plurality of stacked or alternating positive and negative electrodes provide a bipolar configuration for the purpose of increasing the total voltage of the resulting battery pack . The cell 81 contains parallel spaced polymeric electrodes 81a-d made according to the present invention and parallel spaced negative electrodes 83a-d which are parallel on and at a distance from the electrodes 82a-d. The separators 84a-d, which can be made of fiberglass, for example, and contain a suitable electrolyte, are placed between the electrodes 82a-d and 83a-d, as shown.

The electrodes 82a-d and 83a-d and trays 84a-d are housed in an electronically insulating container 85. The container 85 also contains bipolar electronically conductive plates 86, 87 and 88, which divide the container 85 into the four insulated compartments 90, 91, 92 and 93. The electrodes 82a and 83a and the separator 84a are placed in compartment 90. The electrodes 82b and 83b and the separator 84b are placed in the compartment 91. The electrodes 82c and 83c and the separator 84c are placed in the compartment 92. The electrodes 82d and 83d and the separator 84d are placed in the compartment 93. The contact to the two ends of the series stack is provided by the contacts 95 and 96 protruding from the holder 85. Although four electrodes 82a-d and four electrodes 8400207 *

J

51a-83a-d are shown in the illustrated embodiment, it will be appreciated that the number of such electrodes may be less than or greater than four, which number depends on the requirements for the cell 81.

. 5.

Example XXI

The composition of Example VI is used as the positive electrode material in the lithium cell 60, and the design of cell 60 is illustrated in Figure 5. Cell 60 is assembled in a dry argon atmosphere. The polymer composition 61 is electropolymerized on a gold strip serving as contact 65. The thickness of each separator 64 is about 0.5 mm. The traders 64 are soaked with electrolyte, 1M LiClO 4 in propylene-15 carbonate. The negative electrode 62 and the reference electrode 63 are made of lithium. The cell 60 is sandwiched between glass plates 68 and 69 as shown, clamped together and the edges sealed with epoxy 70.

A polymer thin film is prepared according to Example VI except that it is electro-polymerized for a shorter time. The film is tested as the positive electrode in cell 60.

The area density of the film is about 0.1 mg / 2 cm. The discharge takes place with a current of about 0.1 mA -2.

25 cm and is stopped when the potential between the positive electrode 61 and the reference electrode 63 drops to about 1 volt. At this point, the polymer demonstrates a specific capacity of 19 Ah (kg polymer) *.

This cell is repeatedly charged and discharged at constant current conditions and shows good reversibility over more than 200 cycles. The behavior of this cell did not deteriorate despite repeated discharging and repeated overcharging of the cell's 4 - 0 0 2 0 7 - 4 - 52 capacity. The open circuits voltage of this type of cell showed no deterioration when tested over a period of 4 months.

5 Example XXII

The composition of Example XI was used as the positive electrode material in the cell described in Example XXI. A thin electropolymerized film with an area density of about 0.25 mg / cm is discharged with a current 2 of about 0.25 mA / em. Discharge is stopped when the potential between the polymer and the reference electrode drops to about 1 volt. This composition has a specific capacity of 83 Ah (kg polymer) ^.

15

Example XXIII

A porous composition prepared according to Example I is used as the positive electrode material in the cell 20 of Figure 1. The self-supporting film has dimensions of about 2 x 0.8 x 0.1 cm and a weight of about 48 mg. The discharge takes place with a total current of 2 milliamps and is stopped when the total cell voltage (between electrodes 5 and 6) drops to 1 volt. This material demonstrates a specific capacity of about 35 Ah (kg polymer) and can be charged and discharged for more than 220 cycles.

Example XXIV

The composition prepared according to the method of Example XV is used as a positive electrode material in the cell shown in Figure 2. The negative electrode size 8400207

"I

-53-.

The material is lithium and the electrolyte is IM LiCIO, in propylene carbonate. The cell is discharged with a current of 1 mA / cm and the discharge is stopped when the total cell voltage drops to 1 volt. The material has a reversible specific capacity of 57 Ah (kg polymer)

Example XXV

The composition prepared according to the method of Example XVI is used as a positive electrode material in the cell, shown in Figure 2. The negative electrode material is lithium and the electrolyte is 1M LiCIO, in propylene carbonate. The cell is discharged with a current of 1 mA / cm and the discharge is stopped when the total cell voltage drops to 15 1 volts. The cell has a reversible specific capacity of 57 Ali (kg polymer) 1.

Example XXVI

A porous composition, prepared according to Example I, is heat treated at 80 ° C and a pressure of about 1 mm Hg absolute for 12 hours.

Example XXVII 25

Example XXIII is repeated except that the product of Example XXVI is used as the positive electrode material in the cell of Figure 1. This material has a specific capacity of about 57 Ah (kg of poly-30 more) *.

8400207

Claims (307)

A porous electronically conductive composition containing an electropolymerized polypyrrole or a copolymer of a pyrrole, characterized by an apparent density of -3 about 0.01 g.cm to about the bulk density of the polypyrrole or copolymer and a surface area of at least twice the surface of a smooth film with the bulk density of the composition. The composition according to claim 1, characterized in that the composition is heat-treated to increase the electrochemical storage capacity of the composition. 3. A composition according to claim 1 in the form of a homogeneous porous film or of a powder, the particles of which are porous. 4. Porous electronically conductive composition containing at least two members, at least one of which contains the porous electronically conductive composition of claim 1. A composition according to claim 1, characterized in that the density of a composition is from about 0.2-3-3 g.cm to about 0.8 g.cm. 6. A composition according to claim 1, which also contains 25 one little mobile anion, characterized in that it has an average ionic transport number during reduction less than about 0.1. Composition according to claim 6, characterized in that the average transport number is less than 0.05. Composition according to claim 6, characterized in that the anions are organic anions. The composition according to claim 8, characterized in that the inorganic anions are derived from organic sulfates or sulfonates. 10. A composition according to claim 9, characterized in that the sulfates or sulfonates are alkyl, aryl, arylakyl, alkaryl or polyolefin sulfates or sulfonates, each with one or more anionic sites. Composition according to claim 10, characterized in that the anion is derived from an alkyl sulfate with at least four carbon atoms in the alkyl groups. Composition according to claim 11, characterized in that the sulfate is lauryl sulfate. Composition according to claim 6, characterized in that the anion is derived from a sulfated polyhydroxy compound. The composition according to claim 13, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetrasulfate salt or the corresponding acid. 15. A composition according to claim 6, characterized in that the anions are derived from pentavalent phosphorus compounds. Composition according to claim 15, characterized in that the phosphorus compound is phosphate. Composition according to claim 15, characterized in that the phosphorus compound is phosphonate. A composition according to claim 15, characterized in that the phosphorus compound is phosphinate. A composition according to claim 1 or 6, which also contains at least one plasticizer. 20. A composition according to claim 19, characterized in that the plasticizer is a polyhydroxy compound. A composition according to claim 19, characterized in that the plasticizer is a polyalkylene glycol. 8400207 t k - 56 - Composition according to claim 1 or 6, characterized in that it contains a redox species. Composition according to claim 22, characterized in that the redox species is a transition metal complex. A composition according to claim 6, characterized in that the anion is also a plasticizer for the composition. 25. Electronically conductive composition containing electro-polymerized polypyrrole or a pyrrole copolymer, which composition contains one or more low-mobility anions, characterized by an average ionic transport number of the low-mobility anions during reduction less than about 0.1. 26. A composition according to claim 25, characterized in that the composition is heat-treated to increase the electrochemical storage capacity of the composition. '27. Composition according to claim 25, characterized in that the ionic transport number is less than 0.05. 28. The composition of claim 25 in the form of a homogeneous coherent smooth film of bulk density or a uniform porous film of less than the bulk density. 29. A composition according to claim 25, characterized in that the anions are derived from organic sulfates or sulfonates. 30. A composition according to claim 29, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyolefin sulfates or sulfonates, all of which have one or more anionic sites. 31. A composition according to claim 25, characterized in that the anion is an alkyl sulfate with at least 4 carbon atoms in the alkyl group. The composition according to claim 31, characterized in that the alkyl sulfate is lauryl sulfate. 8400207 - 57 - A composition according to claim 25, characterized in that the anion is derived from a sulfated polyhydroxy compound. 34. A composition according to claim 33, characterized in that the sulfated polyhydroxy compound is pentaerythritol ether sulfate sulfur or a corresponding acid. A composition according to claim 25, characterized in that the anions are derived from pentavalent phosphorus compounds. A composition according to claim 35, characterized in that the phosphorus compound is phosphate. A composition according to claim 35, characterized in that the phosphorus compound is phosphonate. 38. A composition according to claim 37, characterized in that the phosphorus compound is phosphinate. A composition according to claim 25, characterized in that it also contains at least one plasticizer. A composition according to claim 39, characterized in that the plasticizer is a polyhydroxy compound. The composition according to claim 39, characterized in that the plasticizer is a polyalkylene glycol. The composition according to claim 25, characterized in that it contains a redox species. 43. A composition according to claim 42, characterized in that the redox species is a transition metal complex. A composition according to claim 25, characterized in that the anion is also a plasticizer for the composition. 45. A method of preparing an electronically conductive polypyrrole or a copolymer of pyrrole, characterized in that the method comprises electropolymerizing a pyrrole or a copolymerizable mixture containing a pyrrole on an electronically conductive surface in an electrolytic bath, which method comprises the steps of: A. immersion of an electronically conductive surface in an electrolytic bath, containing at least one liquid and at least one immiscible liquid or gas or finely divided solid particles, wherein a pyrrole or copolymerizable mixture containing a pyrrole is one of the liquids or is dissolved in at least one of the liquids and B. electric current through the bath at a voltage sufficient to electropolymerize a pyrrole or copolymerizable mixture containing a pyrrole on the electronically conductive surface. 46. A method of preparing an electronically conductive polypyrrole or a copolymer of pyrrole, characterized in that the method comprises electropolymerizing pyrrole or a copolymerizable mixture containing a pyrrole on an electronically conductive surface in an electrolyte bath, which method comprises the steps of A. immersing an electronically conductive surface in an electrolytic bath containing at least one liquid and at least one immiscible liquid or gas, wherein the pyrrole or copolymerizable mixture containing a pyrrole is one of the liquids or is dissolved in at least one of the liquids: 07. and B. passing an electric current through the bath 25 at a voltage sufficient to electropolymerize the pyrrole or copolymerizable mixture containing a pyrrole on the electronically conductive surface. A method according to claim 46, characterized in that the electric current is continuous or varying. A method according to claim 46, characterized in that the bath is stirred when the electric current is passed through the bath. 8400207 - 59 - The method of claim 46, wherein the poly-pyrrole or copolymer of a pyrrole is deposited on the conductive surface. 50. A method according to claim 46, characterized in that the pyrrole polypyrrole or copolymer is formed as a powder on the electronically conductive surface and dispersed in the bath. 51. A method according to claim 46, characterized in that the electrolytic bath contains pyrrole, water and a water-immiscible organic diluent. A method according to claim 51, characterized in that the bath also contains an emulsifying agent. 53. A method according to claim 51, characterized in that the pyrrole polypyrrole or copolymer is formed as a powder on the conductive surface and the powder is dispersed in the bath. 54. A method of preparing an electronically conductive polypyrrole or a copolymer of a pyrrole, the method comprising the steps of: A. electropolymerizing a pyrrole or a copolymerisable mixture containing a pyrrole on an electronically conductive surface in an electrolytic bath by 1. immersing an electronically conductive surface in an electrolytic bath containing (a) an aqueous dispersion - 25 s of pyrrole, or a mixture of the aqueous dispersion and at least one copolymerizable monomer, or (b) a pyrrole or a mixture of a pyrrole and / or at least one copolymerizable monomer, water and a water-immiscible diluent, 2 stirring the bath and 3. passing an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or a pyrrole mixture and deposit the polymer or -; 8400207 • · - 60 - copolymer on the electronically conductive surface, and B. removing the polymer or copolymer from the conductive surface. A method according to claim 54, characterized in that the electrolytic bath is maintained at a temperature of about 15 to 50 ° C when the electric current is passed through the bath. 56. A method according to claim 54, characterized in that the electric current is a continuous or varying electric current. A method according to claim 54, characterized in that the electric current is a direct current. A method according to claim 54, characterized in that the electrolytic bath also contains an emulsifying agent. A method according to claim 54, characterized in that the electrolytic bath contains at least about 50% by weight of water. 60. A method according to claim 45 or 54, characterized in that the electrolytic bath also contains one or more low-mobility anions, which are incorporated in the polypyrrole or copolymer of pyrrol and which are characterized by an average ionic transport number of the low-mobility anions during reduction less than 0.1. 61. A method according to claim 59, characterized in that the ionic transport number is less than 0.05. A method according to any one of claims 45, 46 or 54, characterized by the step of thermally treating the electronically conductive pyrrole polypyrrole or copolymer to increase its electrochemical storage capacity. 63. Process according to claim 60, characterized in that the anions in the bath are derived from organic sulfates or sulfonates. 8400207 - 61 - A method according to claim 63, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyolefin sulfates or sulfonates, all of which have one or more anionic sites. 65. A process according to claim 60, characterized in that the anion is derived from an alkyl sulfate containing at least 4 carbon atoms in the alkyl group. 66. Process according to claim 60, characterized in that the anion is derived from a sulfated polyhydroxy compound. A method according to claim 66, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetra sulfate salt or the corresponding acid. 68. A method according to claim 60, characterized in that the anions are derived from a pentavalent phosphorus compound. 69. A method according to claim 68, characterized in that the phosphorus compound is phosphate. 70. A method according to claim 68, characterized in that the phosphorus compound is phosphonate. 71. A method according to claim 68, characterized in that the phosphorus compound is phosphinate. 72. A method according to claim 45 or 54, characterized in that the bath also contains a plasticizer. A method according to claim 72, characterized in that the plasticizer is a polyhydroxy compound. 74. A method according to claim 72, characterized in that the plasticizer is a polyalkylene glycol. 75. A method according to claim 45 or 54, 30, characterized in that the bath contains a redox species. 76. A process according to claim 75, characterized in that the redox species is a transition metal complex. -84 002 0 7 w r> - 62 - A method according to claim 45 or 54, characterized in that the bath also contains a neutral or ionic surfactant. 78. A process according to claim 60, characterized in that the anion is also a plasticizer for the polypyrrole or copolymer of pyrrole. 79. A method of preparing an electronically conductive polypyrrole or copolymer of pyrrole, said method comprising electropolymerizing pyrrole or a copolymerizable mixture containing pyrrole on an electronically conducting surface in an electrolytic bath, the method comprising the steps of Δ. immersion of an electronically conductive surface in an electrolytic bath containing an aqueous mixture of pyrrole or a mixture of pyrrole and a copolymerizable monomer and water and B. passing an electric current through the bath at a voltage sufficient for electropolymerization of the pyrrole or a copolymerizable mixture containing pyrrole on the electronically conductive surface. A method according to claim 79, characterized in that the bath is stirred when the electric current is passed through the bath. 81. A method according to claim 79, characterized in that the polypyrrole or polypyrrole copolymer is deposited on the electronically conductive surface. 82. A method according to claim 79, characterized in that the polypyrrole or copolymers of pyrrole are formed as a powder on the conductive surface and dispersed in the bath. 83. A process according to claim 79, characterized in that the bath also contains a neutral or ionic surfactant 8400207-63 compound. A method according to claim 79, characterized in that the bath also contains an emulsifying agent. 85. A method according to claim 79, characterized in that the bath also contains one or more low-mobility anions, which are incorporated in the polypyrrole copolymer of pyrrol and which are characterized by an average ionic transport number of the low-mobility anions during reduction less than 0.1. A method according to claim 85, characterized in that the transport number is less than 0.05. 87. A method of preparing an electronically conductive polypyrrole or a copolymer of pyrrole, characterized in that the method comprises the steps of 15 A. electropolymerizing a pyrrole or a copolymerizable mixture containing a pyrrole on an electronically conducting surface. in an electrolytic bath by dipping an electronically conductive surface in an electrolytic bath containing an aqueous mixture of pyrrole or a copolymerizable mixture of pyrrole, water and one or more low mobility anions which are incorporated into the polypyrrole by electropolymerization and which anions are characterized by an average ionic transport number at reduction of less than 0.1, 2. stirring the bath and 3. passing an electric current through the bath at a voltage sufficient for electropolymerizing the pyrrole or pyrrole mixture - Deposition of the polymer or copolymer on the electronically conductive surface, and removing the B. settlement of the conductive surface. 88. A method according to claim 87, characterized in that 8400207 * - - 64 - that the transport number upon unloading is less than 0.05. 89. A method according to claim 87, characterized in that the electrolytic bath is kept at a temperature of about 15 to 50 ° C when the electric current is passed through the bath 5. 90. A method according to claim 87, characterized in that the electric current is a direct current. 91. A method according to claim 79 or 87, characterized in that it comprises the step of thermally treating the electronically conductive pyrrole polypyrrole or copolymer to increase its electrochemical storage capacity. 92. A process according to claim 87, characterized in that the anions in the bath are derived from organic sulfates or sulfonates. 93. A process according to claim 92, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyophenin sulfates or sulfonates, all having one or more anionic sites. 94. A process according to claim 93, characterized in that the anion is derived from an alkyl sulfate, which has at least 4 carbon atoms in the alkyl group. 95. A process according to claim 87, characterized in that the anion is derived from a sulfated polyhydroxy compound. 96. A process according to claim 95, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetra sulfate salt or the corresponding acid. 97. A process according to claim 87, characterized in that the anions are derived from a pentavalent phosphorus compound. 98. A method according to claim 97, characterized in that the phosphorus compound is phosphate, 8400207 -65- 99. A method according to claim 97, characterized in that the phosphorus compound is phosphonate. 100. A method according to claim 97, characterized in that the phosphorus compound is phosphinate. 101. A method according to claim 87, characterized in that the bath also contains a plasticizer. 102. A method according to claim 101, characterized in that the plasticizer is a polyhydroxy compound. 103. A method according to claim 101, characterized in that the plasticizer is a polyalkylene glycol. 104. A method according to claim 87, characterized in that the bath contains a redox species. 105. A method according to claim 104, characterized in that the redox species is a transition metal complex. 106. A method according to claim 87, characterized in that the anion is also a plasticizer for the polypyrrole or copolymer of pyrrole. 107. A method of preparing an electronically conductive polypyrrole or a copolymer of pyrrole, characterized in that this method comprises electropolymerizing a pyrrole or a copolymerizable mixture containing a pyrrole on an electronically conductive surface in an electrolytic bath by A. dipping an electronically conductive surface in an electrolyte bath containing (1) a pyrrole or a mixture of pyrrole with a copolymerizable monomer, (2) one or more low-mobility anions, which are incorporated into the polypyrrole or copolymer of pyrrole, and characterized by an average ionic transport number of the few mobile anions during reduction of the polypyrrole or copolymer less than 0.01, and (3) an organic diluent, and 8400207 <fc - 66 - B. feeding an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or copolymerizable mixture containing pyrrole, on the electronically conductive surface. 108. A method according to claim 107, characterized in that the bath is stirred when the electric current is passed through the bath. 109. A method according to claim 107, characterized in that the pyrrole polypyrrole or copolymer is deposited on the conductive surface. 110. A method according to claim 107, characterized in that the transport number is less than 0.05. 111. A process according to claim 107, characterized in that the bath also contains a neutral or ionic surfactant compound. 112. A method according to claim 107, characterized in that the electrolyte bath is maintained at a temperature of about 15 to about 50 ° C when the electric current is passed through the bath. A method according to claim 107, characterized in that it further comprises the step of thermally treating the electronically conductive pyrrole polypyrrole or copolymer to increase its electrochemical storage capacity. 114. A method according to claim 107, characterized in that the anions in the bath are derived from organic sulfates or sulfonates. 115. Process according to claim 114, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyolefin sulfates or sulfonates, each of which contains one or more ionic sites. 116. Process according to claim 115, characterized in that the anion is derived from an alkyl sulfate which has at least 84 0 02 0 7 * - 67 - 4 carbon atoms in the alkyl group. The method according to claim 107, characterized in that the anion is derived from a sulfated polyhydroxy compound. 5 M8. Process according to claim 117, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetra sulfate salt or the corresponding acid. 119. A method according to claim 107, characterized in that the anions are derived from pentavalent phosphorus compounds. 120. A method according to claim 119, characterized in that the phosphorus compound is phosphate. 121. A method according to claim 119, characterized in that the phosphorus compound is phosphonate. 122. A method according to claim 119, characterized in that the phosphorus compound is phosphinate. 123. A method according to claim 107, characterized in that the bath also contains a plasticizer. 124. A method according to claim 123, characterized in that the plasticizer is a polyhydroxy compound. 125. A method according to claim 123, characterized in that the plasticizer is a polyalkylene glycol. 126. A method according to claim 107, characterized in that the bath contains a redox species. 127. A method according to claim 126, characterized in that the redox species is a transition metal complex. 128. A method according to claim 107, characterized in that the anion is also a plasticizer for the polypyrrole or copolymer of polypyrrole. 129. Electrochemical cell containing polymeric electrode-members containing a porous electronically conductive composition, which composition contains an electropolymerized polypyrrole or a pyrrole copolymer, which composition is characterized by an apparent density of 8400207. about -3 0.01 g / cm to about the bulk density of the polypyrrole or copolymer and a surface area of at least twice the surface area of a smooth film with bulk density of the composition. 130. A cell according to claim 129, characterized in that the polymeric electrode members contain a porous electronically conductive composition, which contains at least two members, at least one of which contains the porous electronically conductive composition. 131. Cell according to claim 129, characterized in that “3 is the density of the composition from about 0.2 g.cm to -3 about 0.8 g.cm. 132. A cell according to claim 129, having the composition which also contains at least a little mobile anion, characterized by an average ionic transport number of the little mobile anions during reduction less than about 0.1. Cell according to claim 132, characterized in that the transport number is less than about 0.05. 134. Cell according to claim 129, characterized in that the composition is heat-treated to increase the electrochemical storage capacity of the composition. 135. A cell according to claim 132, characterized in that the anions are derived from organic sulfates or sulfonates, 136. Cell according to claim 135, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyolefin sulfates or sulfonates, each containing one or more anionic sites. 137. Cell according to claim 132, characterized in that the anion is derived from an alkyl sulfate containing at least 4 carbon atoms in the alkyl group. 138. A cell according to claim 137, characterized in that the sulfate is lauryl sulfate. 8400207 * - 69 - 139. Gel according to claim 132, characterized in that the anion is derived from a sulfated polyhydroxy compound. 140. A cell according to claim 139, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetra sulfate salt or the corresponding acid. 141. Cell according to claim 132, characterized in that the anions are derived from pentavalent phosphorus compounds. 142. Cell according to claim 141, characterized in that the phosphorus compound is phosphate. 143. Cell according to claim 141, characterized in that the phosphorus compound is phosphonate. 144. Cell according to claim 141, characterized in that the phosphorus compound is phosphinate. 145. Cell according to claim 129 or 132, characterized in that the composition also contains at least one plasticizer. 146. A cell according to claim 145, characterized in that the plasticizer is a polyhydroxy compound. 147. Cell according to claim 145, characterized in that the plasticizer is a polyalkylene glycol. 148. Cell according to claim 129 or 132, characterized in that the composition contains a redox species. 149. Cell according to claim 148, characterized in that the redox species is a transition metal complex. 150. Cell according to claim 132, characterized in that the anion is also a plasticizer for the composition. 151. Electrochemical cell containing polymeric electrode members, which polymeric electrode members contain an electronically conductive composition, containing electro-polymerized polypyrrole or a copolymer of pyrrole, which composition contains one or more low-mobility anions, characterized by an average ionic transport number for the low-mobility 8400207 Λ t »- 70 anions during reduction less than approximately 0,1. 152. Cell according to claim 151, characterized in that the transport number is less than 0.05. 153. Cell according to claim 151, characterized in that the composition is heat treated to increase the electrochemical storage capacity of the composition. 154. Cell according to claim 151, characterized in that the anions are derived from organic sulfates or sulfonates. 155. A cell according to claim 154, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyolefin sulfates or sulfonates, each of which contains one or more anionic sites. 156. A cell according to claim 151, characterized in that the anion is an alkyl sulfate containing at least 4 carbon atoms in the alkyl group. 157. A cell according to claim 156, characterized in that the alkyl sulfate is lauryl sulfate. 158. A cell according to claim 151, characterized in that the anion is derived from a sulfated polyhydroxy compound. 159. A cell according to claim 158, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetrasulfate salt or the corresponding acid. 160. A cell according to claim 151, characterized in that the anions are derived from pentavalent phosphorus compounds. 161. A cell according to claim 160, characterized in that the phosphorus compound is phosphate. 162. A cell according to claim 160, characterized in that the phosphorus compound is phosphonate. 163. Cell according to claim 160, characterized in that the phosphorus compound is phosphinate. 164. A cell according to claim 151, characterized in that the composition also contains at least one plasticizer. 8400207 - 71 - 165. Cell according to claim 164, characterized in that the plasticizer is a polyhydroxy compound. 166. A cell according to claim 164, characterized in that the plasticizer is a polyalkylene glycol. 167. Cell according to claim 151, characterized in that the composition contains a redox species. 168. Cell according to claim 167, characterized in that the redox species is a transition metal complex. 169. Cell according to claim 151, characterized in that the anion is also a plasticizer or a composition. 170. Electrochemical cell containing polymeric electrode members, which polymeric electrode members contain an electronically conductive polypyrrole or a copolymer of pyrrole prepared by a method comprising electropolymerizing pyrrole or a copolymerizable mixture containing a pyrrole an electronically conductive surface in an electrolyte bath, the method comprising the steps of A. dipping an electronically conductive surface in an electrolyte bath, containing at least one liquid and at least one immiscible liquid or gas or finely divided solid particles, in which a pyrrole or copolymerizable mixture containing a pyrrole, one of the liquids or dissolved in at least one of the liquids and B. passing an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or copolymerizable mixture , which contains a pyrrole, at the electronically conductive surface. 171. Electrochemical cell containing polymeric electrode members, which polymeric electrode members contain an electronically conductive polypyrrole or a copolymer of pyrrole prepared by a method comprising electropolymerizing a pyrrole or a copolymerizable mixture containing a pyrrole, 8400207 - 72 - i at an electronically conductive surface in an electrolyte bath, the method comprising the steps of: A. dipping an electronically conductive surface in an electrolyte bath, containing at least one liquid and at least one non-miscible liquid or gas, wherein the pyrrole or copolymerizable mixture containing a pyrrole is one of the liquids or is dissolved in at least one of the liquids, and B. passing an electric current through the bath at a voltage sufficient for electropolymerization of 10 the pyrrole or copolymerizable mixture containing pyrrole at the electronically conductive surface. The cell of claim 171, characterized in that the electric current is continuous or varying. 173. Cell according to claim 171, characterized in that the bath is stirred when the electric current is passed through the bath. Cell according to claim 171, characterized in that the polypyrrole or copolymer of a pyrrole is deposited on the conductive surface. The cell of claim 171, characterized in that the polypyrrole or copolymer of a pyrrole is formed as a powder at the electronically conductive surface and dispersed in the bath. 176. Cell according to claim 171, characterized in that the electrolyte bath contains pyrrole, water and a water-immiscible organic diluent. Cell according to claim 176, characterized in that the bath also contains an emulsifying agent, 178. Cell according to claim 171, characterized in that the polypyrrole or copolymer of the pyrrole is formed as a powder at conductive surface and the powder is dispersed in the bath. 8400207 • * - 73 - 179. An electrochemical cell containing polymeric electrode members containing polymeric electrode members electronically conductive pyrrole polypyrrole or copolymer prepared by a method comprising the steps of 5 A. electropolymerizing the pyrrole or a copolymerisable mixture, which a pyrrole, at an electronically conductive surface in an electrolyte bath by 1. dipping an electronically conductive surface in an electrolyte bath, which contains (a) an aqueous dispersion of a pyrrole or a mixture of the aqueous dispersion and at least one copolymerizable monomer, or (b) a pyrrole or a mixture of a pyrrole and / or at least one copolymerizable monomer, water and a water-immiscible diluent, 2. stirring the bath, and 3. passing an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or a pyrrole mixture and deposit the polymer or copolymer on the electronically leading surface, and B. removing the polymer or copolymer from the conducting surface. The cell of claim 179, characterized in that the electrolyte bath is maintained at a temperature of about 15 to 50 ° C when the electric current is passed through the bath. 181. Cell according to claim 179, characterized in that the electric current is a continuous or varying electric current. A cell according to claim 171, characterized in that the electric current is a direct current. 183. A cell according to claim 179, characterized in that the electrolyte bath also contains an emulsifying agent. The cell of claim 179, characterized in that 8400207 * * V-74 - the electrolyte bath contains at least about 50% by weight water. 185. A cell according to claim 170 or 179, characterized in that the electrolyte bath also contains one or more low-mobility anions which are incorporated in the polypyrrole or copolymer of pyrrol and which are characterized by an average ionic transport number of the low-mobility anions. during reduction less than 0.1. 186. Cell according to claim 185, characterized in that the transport number is less than 0.05. 187. A cell according to any one of claims 170, 171 or 179, characterized in that the electronically conductive pyrrole polypyrrole or copolymer is heat treated to increase its electrochemical storage capacity. 188. A cell according to claim 185, characterized in that the anions in the bath are derived from organic sulfates or sulfonates. 189. Cell according to claim 188, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or polyolefin sulfates or sulfonates, each containing one or more anionic sites. 190. Cell according to claim 185, characterized in that the anion is derived from an alkyl sulfate containing at least 4 carbon atoms in the alkyl group. 191 ·. Cell according to claim 185, characterized in that the anion is derived from a sulfated polyhydroxy compound. 192. Cell according to claim 191, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetrasulfate salt or the corresponding acid. 193. Cell according to claim 185, characterized in that the anions are derived from pentavalent phosphorus compounds. 194. A cell according to claim 193, characterized in that the phosphorus compound is phosphate. 8400207 - 75 - The cell of claim 193, characterized in that the phosphorus compound is phosphonate. 196. A cell according to claim 193, characterized in that the phosphorus compound is phosphinate. 197. Cell according to claim 170 or 179, characterized in that the bath also contains a plasticizer. 198. Cell according to claim 197, characterized in that the plasticizer is a polyhydroxy compound. 199. Cell according to claim 197, characterized in that the plasticizer is a polyalkylene glycol. 200. Cell according to claim 170 or 179, characterized in that the bath contains a redox species. 201. A cell according to claim 200, characterized in that the redox species is a transition metal complex. 202. Cell according to claim 170 or 179, characterized in that the bath also contains a neutral or ionic surfactant. 203. Cell according to claim 184, characterized in that the anion is also a plasticizer for the polypyrrole or copolymer of pyrrole. 204. Electrochemical cell containing polymeric electrode members containing polymeric electrode members electronically conductive polypyrrole or a copolymer of pyrrole prepared by a method comprising electropolymerizing pyrrole or a copolymerizable mixture containing pyrrole in an electronic conductive surface in an electrolyte bath, comprising the steps of A. dipping an electronically conductive surface in an electrolyte bath, which contains an aqueous mixture of pyrrole or a mixture of pyrrole and a copolymerizable monomer and water and B. passes electric current the bath at an 8400207. ψ - 76 - * V; voltage sufficient to electropolymerize the pyrrole or copolymerizable mixture containing a pyrrole at electronically conductive surface. 205. Cell according to claim 204, characterized in that the bath is stirred when the electric current is passed through the bath. 206. A cell according to claim 204, characterized in that the pyrrole polypyrrole or copolymer is deposited on the electronically conductive surface. 207. Cell according to claim 204, characterized in that the pyrrole polypyrrole or copolymer is formed as a powder at the conductive surface and dispersed in the bath. 208. Cell according to claim 204, characterized in that the bath also contains a neutral or ionic surfactant. 209. Cell according to claim 204, characterized in that the bath also contains an emulsifying agent. 210. Cell according to claim 204, characterized in that the bath also contains one or more low-mobility anions which are incorporated in the polypyrrole or copolymer of pyrrol and which are characterized by an average ionic transport number of the low-mobility anions during reduction. less than 0.1. 211. Cell according to claim 210, characterized in that the transport number is less than 0.05. 212. Electrochemical cell containing polymeric electrode members, containing polymeric electrode members electronically conductive pyrrole polypyrrole or copolymer, prepared by a method comprising the steps of A, electropolymerizing a pyrrole or a copolymerizable mixture of a pyrrole at an electronically conductive surface 8400207 + ι - 77 - in an electrolytic bath by 1. immersing an electronically conductive surface in an electrolyte bath containing an aqueous mixture of pyrrole or a copolymerizable mixture of pyrrole, water and one or 5 more low-mobility anions, which are incorporated into the polypyrrole by electropolymerization, and which anions are characterized by an average ionic transport number of the low-mobile anions on reduction less than 0.1, 2. stirring of the bath, and 3. feeding of an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or pyrrole mixture and deposition of polymer or copolymer on the electronically conductive surface, and B. removal of deposition from the conductive surface. 213. A method according to claim 212, characterized in that the transport number is less than 0.05. 214. A cell according to claim 212, characterized in that the electrolyte bath is maintained at a temperature of about 20 to 50 ° C when the electric current is passed through the bath. 215. A cell according to claim 212, characterized in that the electric current is a direct current. 216. Cell according to claim 204 or 212, characterized in that the electronically conductive pyrrole polypyrrole or copolymer is heat-treated to increase its electrochemical storage capacity. 217. Cell according to claim 212, characterized in that the anions in the bath are derived from the organic sulfates or sulfonates. 218. Cell according to claim 217, characterized in that the sulfates or sulfonates are alkyl, aryl, arylalkyl, alkaryl or 8400207 * - 78 - polyolefin sulfates or sulfonates, each containing one or more anionic sites. 219. A cell according to claim 212, characterized in that the anion is derived from an alkyl sulfate having at least 4 carbon atoms in the alkyl groups. 220. A cell according to claim 212, characterized in that the anion is derived from a sulfated polyhydroxy compound. 221. A cell according to claim 220, characterized in that the sulfated polyhydroxy compound is pentaerythriltol tetrasulfate salt or the corresponding acid. 222. A cell according to claim 212, characterized in that the anions are derived from pentavalent phosphorus compounds. 223. Cell according to claim 222, characterized in that the phosphorus compound is phosphate. 224. Cell according to claim 222, characterized in that the phosphorus compound is phosphonate. 225. A cell according to claim 222, characterized in that the phosphorus compound is phosphinate. 226. A cell according to claim 212, characterized in that the bath also contains a plasticizer. 227. A cell according to claim 226, characterized in that the plasticizer is a polyhydroxy compound. 228. A cell according to claim 226, characterized in that the plasticizer is a polyalkylene glycol. 229. Cell according to claim 212, characterized in that the bath contains a redox species. The cell of claim 229, characterized in that the redox species is a transition metal complex. 231. Cell according to claim 212, characterized in that the anion is also a plasticizer for the polypyrrole or copolymer of pyrrole. 232. Electrochemical cell, containing polymeric electrode 8400207 *. Contains members which contain polymeric electrode members electronically conductive polypyrrole or copolymer of pyrrole prepared by a method comprising electropolymerizing a pyrrole or a copolymerizable mixture containing a pyrrole at an electronically conductive surface in an electrolyte bath by A. dipping an electronically conductive surface in an electrolyte bath containing (1) pyrrole, or a mixture of pyrrole and a copolymerizable monomer, 10 (2) one or more low-mobility anions, which are incorporated into the polypyrrole or copolymer of pyrrole and characterized by an average ionic transport number of the low-mobility anions during reduction of a polypyrrole or copolymer less than 0.1, and 15 (3) an organic diluent, and B. passing an electric current through the bath at a voltage sufficient to electropolymerize the pyrrole or copolymerizable mixture containing pyrrole in the process of electronically conductive surface. 233. Cell according to claim 232, characterized in that the bath is stirred when the electric current is passed through the bath. 234. Cell according to claim 232, characterized in that the pyrrole polypyrrole or copolymer is deposited on the conductive surface. 235. Cell according to claim 232, characterized in that the transport number is less than 0.05. 236. Cell according to claim 232, characterized in that the bath also contains a neutral or ionic surfactant compound. 237. Cell according to claim 232, characterized in that the electrolyte bath is kept at a temperature of about 8400207 - 80-15 to about 50 ° C when the electric current is passed through the bath. 238. Cell according to claim 232, characterized in that the electronically conductive polypyrrole or copolymer of pyrrole 5 is heat-treated to increase its electrochemical storage capacity. 239. Cell according to claim 232, characterized in that the anions in the bath are derived from organic sulfates or sulfonates. 240. Cell according to claim 239, characterized in that the sulphates or sulphonates are alkyl, aryl, arylakyl, alkaryl or polyolefin sulphates or sulphonates, each of which contains one or more anionic sulphates. 241. Cell according to claim 240, characterized in that the anion is derived from an alkyl sulfate containing at least 4 carbon atoms in the alkyl group. 242. Cell according to claim 241, characterized in that the anion is derived from a sulfated polyhydroxy compound. 243. Cell according to claim 242, characterized in that the sulfated polyhydroxy compound is pentaerythritol tetrasulfate salt or the corresponding acid. 244. A composition according to claim 232, characterized in that the anions are derived from pentavalent phosphorus compounds. 245. A composition according to claim 232, characterized in that the phosphorus compound is phosphate. 246. A composition according to claim 232, characterized in that the phosphorus compound is phosphonate. 247. A composition according to claim 232, characterized in that the phosphorus compound is phosphinate. 248. Cell according to claim 232, characterized in that the bass also contains a plasticizer, 8400207 - 81 - •. 249. Cell according to claim 248, characterized in that the plasticizer is a polyhydroxy compound. 250. Cell according to claim 248, characterized in that the plasticizer is a polyalkylene glycol. 251. Cell according to claim 232, characterized in that the bath contains a redox species. 252. Cell according to claim 251, characterized in that the redox species is a transition metal complex. 253. Cell according to claim 232, characterized in that the anion is also a plasticizer for the polypyrrole or copolymer of pyrrole. 254. Electrochemical cell containing negative metal electrode members, separator members, electrolyte members and positive polymer electrode members, which positive polymer electrode members contain a porous electronically conductive composition containing an electropolymerized polypyrrole or copolymer of a pyrrole , which composition is characterized by. -3 an apparent density of about 0.1 µm to about the bulk density of the polypyrrole or copolymer and a surface of at least twice the surface of a smooth film with a bulk density of the composition. 255. A cell according to claim 254, characterized in that the negative electrode members contain an alkali metal, an alkaline earth metal or an alloy of the alkali metal or alkaline earth metal. 256. Cell according to claim 254, characterized in that the negative electrode members contain a material selected from the group consisting of lithium, sodium, potassium, magnesium, calcium or an alloy thereof. 257. Cell according to claim 254, characterized in that the composition is heat-treated to increase the electrochemical storage capacity. 8.4 0 0 20 7 ^ t 4 »t»> - 82 - 258. Cell according to claim 254, characterized in that the positive polymer electrode members provide an increased resistance barrier to cell damage due to over-discharge. 259. Cell according to claim 254, characterized in that the composition is cold pressed to provide the positive polymeric electrode members. 260. A cell according to claim 254, characterized in that the composition contains binders, which composition is cold pressed to provide the positive polymeric electrode members. 261. Cell according to claim 254, characterized in that electrical contact is made with the positive polymeric electrode member through sieve members or members placed between the positive polymeric electrode member and the separator member. 262. Cell according to claim 254, characterized in that the positive polymer electrode member contains at least one other redox species. 263. Electrochemical cell, which contains a separator member, an electrolyte member, a negative polymer electrode member and another electrode member, which other electrode member is electrochemically more positive than the negative polymer electrode member, which negative polymer electrode member is a porous Contains an electronically conductive composition containing an electropolymerized pyrrole polypyrrole or copolymer, which composition is characterized by an apparent density of -3 about 0.1 g.cm to about the bulk density of the polypyrrole or copolymer and a surface has at least twice the surface area of a smooth film with a bulk density of the composition. 264. Cell according to claim 263, characterized in that 8400207 p '. n. The composition is treated thematically to increase its electrochemical storage capacity. 265. Cell according to claim 263, characterized in that the negative polymer electrode member provides an increased resistance barrier to cell damage due to overcharge. 266. Cell according to claim 263, characterized in that the composition is cold pressed to provide the negative polymer electrode member. 267. Cell according to claim 263, characterized in that the negative polymer electrode member contains binders, which composition is cold pressed to provide the negative polymer electrode member. 268. Cell according to claim 263, characterized in that electrical contact with the negative polymeric electrode member is through a sieve or grating member disposed between the negative polymeric electrode member and the separator member. 269. Cell according to claim 263, characterized in that the negative polymer electrode member contains at least one other redox species. 270. Electrochemical cell, comprising: a separator; an electrolyte member; a positive polymer electrode member and a negative polymer electrode member; the positive polymeric electrode member contains a first composition; the negative polymeric electrode member contains a second composition; the first composition and the second composition each contain a porous electronically conductive material which contains an electro-polymerized polypyrrole or copolymer of a pyrrole, which material is characterized by an apparent density of about -3 0.1 g.cm to about bulk density of the polypyrrole or copolymer and a surface area of at least twice the surface area 8400207 4. - 84 - α * ttt of a smooth film with a bulk density of the composition. 271. Cell according to claim 270, characterized in that the first composition and / or the. second composition is heat treated to increase the electrochemical storage capacity. The cell of claim 270, characterized in that the positive polymeric electrode member provides an increased resistance barrier to cell damage due to over-discharge. 273. Cell according to claim 270, characterized in that the first composition is cold-pressed to provide the positive polymeric electrode member and / or the second composition is cold-pressed to provide the negative polymeric electrode member. 274. Cell according to claim 270, characterized in that the first composition contains a binder, which first composition is cold-pressed to provide the positive polymer electrode member and / or the second composition contains a binder, which second composition is cold-pressed Providing the negative polymeric electrode member. 275. A cell according to claim 27Q, characterized in that electrical contact is made with the positive polymeric electrode member through a screener or grid member disposed between the positive polymeric electrode member and the separator member; and / or wherein electrical contact with the negative polymeric electrode member is through a screener or grid member disposed between the negative polymeric electrode member and the separator member. 276. Cell according to claim 270, characterized in that the positive polymeric electrode member and / or the negative polymeric electrode member contains at least one other redox species. 277. Electrochemical cell containing a negative metal electrode member, a separator member, an electrolyzer member and a positive polymer electrode member, the positive polymer electrode member containing a composition which is electro-polymerized polypyrrole or a pyrrole copolymer, which composition contains one or more low-mobility anions, characterized by an average ionic transport number of the low-mobility anions during reduction less than about 0.1. The cell of claim 277, characterized in that the transport number is less than about 0.01. 279. Cell according to claim 277, characterized in that the negative electrode member contains an alkali metal, alkaline earth metal, or an alloy of an alkali metal or alkaline earth metal. 280. A cell according to claim 277, characterized in that the negative electrode member contains a material selected from the group consisting of lithium, sodium, potassium, magnesium, calcium or an alloy thereof. 281. Cell according to claim 277, characterized in that the composition is heat-treated to increase the electrochemical storage capacity. 282. Cell according to claim 277, characterized in that the positive polymer electrode member provides an increased resistance barrier to cell damage due to over-discharge. 283. Cell according to claim 277, characterized in that the composition is cold pressed to provide the positive polymeric electrode member. 284. Cell according to claim 277, characterized in that the composition contains a binder, which composition is cold pressed to provide the positive polymeric electrode member. 285. Cell according to claim 277, characterized in that electrical contact with the positive polymeric electrode member 84 0 02 0 7 α - 86 - Λ ψ • - t · <. takes place through a screener or grating member disposed between the positive polymeric electrode member and the separator member. 286. Cell according to claim 277, characterized in that the positive polymer electrode member contains at least one other redox species. 287. An electrochemical cell containing a separator member, an electrolyte member, a negative polymer electrode member and another electrode member, which other electrode member 10 is more electrochemically positive than the negative polymer electrode member, the negative polymer electrode member a composition containing an electro-polymerized polypyrrole or a pyrrole copolymer, which composition contains one or more low-mobility anions, characterized by an average transport number for the low-mobility anions during reduction less than 0.1. 288. Cell according to claim 287, characterized in that the transport number is less than about 0.01. 289. Cell according to claim 287, characterized in that the composition is heat-treated to increase the electrochemical storage capacity. 290. Cell according to claim 287, characterized in that the negative polymer electrode member provides an increased resistance barrier to cell damage due to over-discharge. 291. Cell according to claim 287, characterized in that the composition is cold pressed to provide the negative polymeric electrode member. 292. Cell according to claim 287, characterized in that the composition contains a binder, which composition is cold pressed to provide the negative polymeric electrode member. 8400207 f '«*» a. Η t »- 87 - 293. Cell according to claim 287, characterized in that the electrical contact with the negative polymeric electrode member is through a screener or grid member disposed between the negative polymeric electrode member and the separator member. 294. Cell according to claim 287, characterized in that the negative polymer electrode member contains at least one other redox species. 295. Electrochemical cell, which contains: a separator-member, an electrolyte member, a positive polymer electrode member and a negative polymer electrode member, the positive polymer electrode member containing a first composition? the negative polymer electrode member contains a second composition; the first composition and the second composition both contain electropolymerized polypyrrole or a pyrrole copolymer containing one or more low-mobility anions, characterized by an average ionic transport number of the low-mobility anions during reduction less than about 0.1. 296. Cell according to claim 295, characterized in that the transport number is less than about 0.01. 297. Cell according to claim 295, characterized in that the first composition and / or the second composition is heat treated to increase the electrochemical storage capacity. 298. Cell according to claim 295, characterized in that the positive polymer electrode member provides an increased resistance barrier to cell damage due to over-discharge and / or the negative polymer electrode member provides an increased resistance barrier to damage. of the cell 30 due to overcharge. 299. Cell according to claim 295, characterized in that the first composition is cold pressed to provide the 8400207 • F. ^ Positive - polymeric electrode member and / or the second composition is cold pressed to provide the negative polymeric electrode member. 300. Gel according to claim 295, characterized in that the first composition contains a binder, the first composition is cold pressed to provide the positive polymer electrode member and / or wherein the second composition contains a binder, which second composition is cold pressed to provide the negative polymeric electrode member. 301. A cell according to claim 295, characterized in that the electrical contact with the positive polymeric electrode member is through a screener or grid member disposed between the positive polymeric electrode member and the separator member; and / or wherein electrical contact with the negative polymeric electrode member is through a screener or grid member interposed between the negative polymeric electrode member and the separator member. 302. Cell according to claim 295, characterized in that the positive polymeric electrode member and / or the negative polymeric electrode member contains at least one other redox species. 303. Cell according to any one of claims 129, 152, 170, 179, 204, 212 or 232, characterized in that the polymeric electrode member comprises a positive polymeric electrode member. 304. A cell according to any one of claims 121, 152, 170, 25, 179, 204, 212 or 232, characterized in that the polymeric electrode member comprises a negative polymer electrode member. 305. Cell according to any one of claims 129, 152, 170, 179, 204, 212 or 232, characterized in that the polymeric electrode member comprises a positive polymeric electrode member and a negative polymeric electrode member. 306. Primary battery, which contains polymeric electrode members, which leaked red members contain the composition according to 8400207 "9 - 89 - a claims 1 or 25. 307. Secondary battery, characterized in that this battery comprises polymeric electrode members, which electrode members contain the composition according to claim 1 or 25. 308. Primary battery, characterized in that it contains polymeric electrode members, which electrode members contain the product of the method according to any one of claims 45, 46, 54, 79, 87 or 107. 309. Secondary battery, characterized in that the battery contains polymeric electrode members, which electrode members contain the product of the method according to any one of claims 45, 46, 54, 79, 87 or 107. 310. The invention as described in the description and / or illustrated in the examples. 8400207