DE1671737A1 - Electrodes for electrochemical power generators based on organic semiconductors - Google Patents

Description

Dr.-lng. by ICreisler Dr.-frtL

Dr.-Infl. Th. Meyer Dr. Feet

Cologne, Pilchnwnhlwui IR 7 17 "3 7

Cologne, (3en February 15, 1968 Ke / lx / Hz

NATIONAL PE_ LA_ RECHERCHE ^ SCIENTIPIQtJE

- ^s (France) -.

Electrodes for electrochemical power generators on the Based on organic semiconductors

The invention relates to accumulators _y the Sindo prepared using organic semiconductors

In this specification the term "more organic" means Semiconductor "; any; macromolecular organic compound., the at the same time electronic conductivity in Has connection with ionic conductivity,

The only Peststoffe was used previously for the production of traditional accumulators metals or inorganic compounds, for "B, metals, non-stöchioiietrisehe oxides or hydroxides of lead, cadmium, Kicke1, silver Odei · zinc ₅ or materials having the partial salt character, · z _o B «the non-sterile lead sulfate,. = ■ .._."

It is also known that the performance of the accumulators, are limited and that they can be found in numerous cases not suitable for certain practical applications where with regard to the space requirements made high demands will- . ■ "-.,;" .-- -

The invention relates to a new type of accumulator eng organic semiconductors can be used. the The invention relates in particular to accumulators with niecri-

109839/0310 _{BAÖ 0} RGNAt

gen manufacturing price, the components of which in large Ker.tj; are available in Handel- Furthermore, the battery, ία Ir. te ren verv.en.det be verv.en.det according to the invention for new applications in which the classic accumulators were not usable. This is achieved according to the invention by electrodes which he which is inserted a metallic conductor and an electrolytic viäZriges ¹ medium between. · At least one organic semiconductor of the above type in fixed-Perm ^ Lalien.

The invention also relates to electrochemical Stroner-A ceugei ", the at least one electrode of the above Kind included,.

The organic semiconductors are for the most part in themselves known materials, which are made from polyconjugated or £ oni. ": ol; en Connections are obtained =. According to the invention v.cruen the properties of the semiconductor of these - organic,! "toi exploited, which stuck to their oxidative cheeses are bound.

To illustrate the state of the art regarding materials suitable for the purposes of the invention; take the work of ¥, as an example. Cristofini, £ R. de Surville, U, Jozefowicz, 1.2, Yu, R, Euvet (OcR, Acad. Sc, rr. (1966) _f 263, 206, 209), which describes the preparation of certain bolyanilines, and the "Jr" work by Mo Jozefowicz and L, T-. Xu (Rev, S6n> Elec, ('S £ 0) ■ 75, 1008 ff.), Which concern the properties of these products.

Information on other organic semiconductors can also be found in the dissertation by J, Perichon (January 1967, Paris).,

It has already been suggested certain types of organic Semiconductors for the production of electro-chi. see power generators to use, for example,

ORIGINAL

writes U.S. Patent 3,110,630 <Du Fönt de i; er.curs) non-aqueous' bstteries that contain electrodes » their active material from organic charge transfer complexes, In particular, these batteries consist of complexes based on tetracyanoquinodimethane if the electrolyte is a non-aqueous Ilediun, thus the charge transport.-effective in the electrode press can take place-,. - "-

Further publications of the prior art, ζ Bc the USA patents 2 83V 045 and 3 '65 590; ' describe accumulators, -in which polymeric materials söge-- Μ called Eedox-off. exchangers are used, electron exchange resins from the group of Hydrochiiionpol ^ neren and their derivatives.

For the purposes of the invention, on the other hand, our own cnef ~. exploited by macromolecular organic substances, the ionic conductivity at the same time and a sufficient electronic conductivity, i.e. about 'C Ohm' -Om exhibit under the operating conditions «

The presence of the electron conduction in this. "Materialienbedeutet that they can accept all. Oxydationszwischenstufen ^l ™ between two extremes, and gives them a Faradaysehe _capacity} the ausnutsbcr is = This, however, only with on the one acceptable power charge-discharge can be recycled, if the material in its mass simultaneously exhibits the two properties of electron conduction and ionic conduction. ”In the palli in which the electrode material exhibits both types of conduction at the same time, the transformation can take place in the entire mass and not just obscurally.

109 839/0310 '■ .-' ■ Λ 6ad original

It has already been proposed to artificially realize the combination of these two types of conduction; by intimately mixing a material / that has redox exchange properties, but is too little an electron conductor, with a powder that has high electron conduction, but is electrochemically inactive, z _o i3o graphite powder =.

The invention relates to the production of electrodes from a material that is at the same time highly electronic

-6 - ^Λ - '<■ see conductivity above 10 ohms »cm', preferably

^ between TO and 10 ² Ohm ~ '= cm ~, and also has high ion conductivity, the conductivities in the order of magnitude of the classical. Elektrolvte corresponds to ,

—Λ - 1 *
d Ji, above VO Ohm, cm "'.

An aqueous electrolytic medium is also used for an electrode according to the invention. If, namely, the organic polymer semiconductors are manufactured in the conventional manner, their ... conductivity remains generally very low or zero, because the ones obtained. Materials are in a neutral state. Therefore, these materials become saturated with water according to the invention and placed with respect to their inner acidity into Eq ei cn ge \ vi ent ge-P by being brought into Eerührung with aqueous buffer solutions = _r was detected. that the ionic conductivity and the electronic conductivity are considerably increased in this way *

Suitable aqueous electrolytic media are either buffered free aqueous readings of sufficient quantities line ■ or!,! noble of the same type, which in a porous structure or immobile due to a gel-forming substance or ion exchange membranes, you have swelled by the aqueous electrolyte,

109839/0310 ^ßAD

187T? 37

. Ton have the products that simultaneously die.im scope of the invention the properties required, d ~ h _a of the polymers which have electronic conductivity and ion conductivity at the same time, the following classes can be mentioned:

1) The products of oxidation of aniline and aromatic

from
Amines substituted on the nitrogen or on the benzene ring

of anilines (toluidine, xylidine, etc.) or polynuclear, substituted or unsubstituted amines, ζ J and aminoanthracenes. : -. ■■■ -

Naphthylanines

The oxidation reactions carried out under these conditions have the formation of new "bonds between the Nitrogen atoms and the sing

result according to the scheme

HH - H +

-ΜΗ

This reaction is accomplished through the formation of Quinone imine cores according to the scheme

-ITH-

or from rings according to the scheme

These oxidation reactions thus lead to the formation of Polymers; in the present description with the

109839/0310

ORIGINAL

167T737

Term "polyanilines" can be referred to and in different ways Amount proportions depending on the oxidizer.

the
degree of active functional groups.

-HIi

9- VI = -

and

-IT =

contain »The • term" polyanilines "also includes substituted polyanilines» For example, I-oly-lT-ii.ethylanilines used to represent products obtained by oxidative polycondensation, of H-Nethylaniline with alkali persulphates in normal aqueous sulfuric acid The polyanilines can be beneficial for the purposes of the invention are used,

2) The polymers obtained by reacting hydroquinene, such as hydroxyanthraquinones (I), with anhydrides of aromatic acids, for example anhydrides of dicarboxylic acids of benzene or naphthalene, which contain group (Ii) _P

can be obtained. 0

(D

(II)

"C = O

• Π.Τ

These reactions lead to the formation of polymeric Irodukten, unterschiedlichein of degree of polymerization by combining the aromatic rings and the reducing "are η .and with oxidizable -OH group-substituted functional groups (III) - _e These polymeric compounds have the necessary · properties, particularly after equilibration with basic or acidic aqueous solutions * your overall conductivity is of the order of ⁵ 1CT OhKf ¹ cm "'in the neutral Z.ustand and can be obtained by equilibration in a buffered aqueous medium by several orders of magnitude increase _L.

© AD

3 / The polymeric products obtained by Polykondensatioiisreaktionen between resorcinol (I) and an aromatic acid dianhydride in the presence of a catalyst such as Zinkchloridj be obtained at 200 ⁰ C, and the polishing products obtained by polycondensation between hydroquinone (II), phthalic anhydride (III) and pyromellitic anhydride (IV) can be obtained in different I.Iengenverhältnisse at 20O ⁰ C,

These polymers or copolymers are associated with the Sarauel term "Polyxanthene" denotes »Their structures are different and depend on the conditions of their manufacture.An example of such structures is schema tis; ^ h represented by (V); .

These polymeric compounds have conductivity "between 10 ~ 'and 10 ~ ohms"" \ cm" ¹ depending on their physical-cheric state, in particular the conditions under which their equilibrium in the buffered aqueous medium has been established «

109839/0310

4) The polymers whose unit consists of a phthalocyanine of different degrees of polymerization ", and dicbeispiel'e by converting a metal or iCecallchlorids with urea and pyromellitic acid (or pyror.:ellitic dianhydride or with a pyromellitic acid nitrile) »These products are also suitable for the purposes of the invention and can be used for electrochemical Purposes to be used «, as a specific example Of these products, the polyphthalocyanine of copper can be mentioned. Depending on their physico-chemical state the conductivity is in the range of 10 to 10 ohms -, cn.- ,. ■ .. -

5) The polycondensates which organic sulfur by reacting at 150 ° to 200 ⁰ C with various compounds such as aromatic amines, phenols, aminophenols !!, polyamines. Polyphenols, naphthylamine, etc., are obtained. Depending on the compounds used and the physico-chemical conditions used, the conductivity of these compounds is between ".0 ~~ and 10" ⁶ ohm ""'.cm" ¹ \ ■

6) The polycondensates of Ferro ce η and a reactive group organic. Compound such as formaldehyde or acetone. The conductivity of the polycondensates of Perrocene with an Oarbonylderivat is between 10 "° and '0 ~" Ohn Ό

cm 'depending on the one used. Aldehyde and the production conditions _o

7) The Schiff's polybases, which are produced by polycondensation made of p-phenylenediamine with a dicarbonyl compound have been and under certain conditions Γΐ ^ επ-shafts which make them suitable for the purposes of the invention. For example, the overall conductivity is of the product obtained from glyoxal, in the neutral state at about 10 ohm Ό cm Ό "" you varied by several orders of magnitude if one considers the acid ease d of the received material changes,

109839/0310

8) The polyhydrazones or polyazines produced by polycondensation can be obtained from hydrazine with a dicarbony derivative * The total conductivity of the from glyoxal

O = CH-CH = Q obtained polyazine is about 10 cm "in the neutral state and can be several orders of magnitude change when changing the acid-base state.

9) Certain polymeric products of the condensation reactions of isatin chloride with thioindoxyl or with hydroxybenzcarbazole, zj = the brown indanthrene dyes or the black indanthrene dyes ο under normal conditions the specific resistance lies in their production of black indanthrene dyes in the order of magnitude -

-8-1-1
voltage voiriO Ohm cm, They can change by several orders of magnitude if the physico-chemical conditions of their production are changed

10) The polymeric products produced by polycondensation between an aromatic amine and a quinone? whose Structure shown schematically by the formula (I) can be obtained = For example, the products have polycondensation with benzidine, (II) total conductivities on the order of 10 ".0hm '.ca in normal State, but it is possible to increase them by several orders of magnitude to change when looking at their acid-base state or changed their physicochemical state

(D

(II)

11) The products of condensation between chloranil and an aromatic diamine in the presence of a catalyst, such as copper acetate, for example results in the implementation of

10003 9 / 031ß

BATHROOM OBlQIKAL

Chloranil with benzidine a polymer whose structure can be shown schematically as follows:

E. , O Cl A * ι ι N AC ,- H

, -10,

The conductivity of this compound is from about ¹ O Ohm cm, but can have the physical-chemical state can be increased by several orders of magnitude by changing the base Zustanues acid "

12) The products of the pyrolysis "of tetraiodopyrrole (I) ₅ triiodiaidazole (II), tetraiodimidazole, with the collective term polypyrrole and polyimidazole designated» Under normal manufacturing conditions they have total ^{conductivity between *! 0 ~ 1} and. '.O * "' ⁰ OhYes " ^: . cm" ¹ _a

(II)

13) The product obtained by the polymerization of 4-chloropyridine (according to the method of Berlin and co-workers, Eokl, / kcd Nauk SSSR, -J4Q * 598 (1-961)) ", and its overall structure can be represented by the following formula:

Cl--

The conductivity of the polymer produced under these conditions is about 10 "" ^ ⁶ ^^ ^Ms Ohra "" .cn ^"and changes by several orders of magnitude if one changed its physico-chemical ^state!

H) The polymeric compounds obtained when. Hitrobenzene or bitrophenol is added in the synthesis of indulins, which belong to the class of products identified by the collective term "Mgrosine" _:

15) The polymeric diazo compounds obtained from bensidine (I) and the γ-acid (II) or 2-aniino-8-naphthol-6-sulfonic acid in an alkaline medium, ζ, Β. _: Dianine black ΓΛ: ■ _0H

As already mentioned, an electrode according to the invention contains at least one organic semiconductor in a solid core. Solid materials of small thickness are preferably used, in particular from a fraction of a millimeter to a few millimeters. As is generally known in electrochemistry, it is possible and even advantageous to connect a certain number of electrodes, which are designed according to the invention, in series. In general, used in a single electrode, the solid organic M semiconductor material in the least possible thickness to _f Chmseiie losses vermeiden-

The solid materials according to the invention can, for example, be processed in the form of granules by simple pressing . It is also possible to combine the powdered organic semiconductors with a plastic binder, a collodion solution or a polystyrene solution in eenzene, whereupon the solid impregnated with the binder is pressed becomes, -to greater evenness. fell. It is also possible to use the solid organic

109839/0310

Semiconductors in connection with flexible polymeric membranes, materials made of cellulose fibers and natural fibers as well as with r.al:romolecular substances such as silicones, gelatine etc. to use-. In addition, depending on the production method of the organic semiconductor, one can immediately obtain fibers into which the polymeric semiconductor is impregnated or onto which this semiconductor is grafted. These methods are known as "coloring the fiber" . . this catfish can be obtained from materials that can be used in electrochemical power generators in physically very different forms, e.g. in the form of powders, substances, Γο-lien, etc. Furthermore, according to the teachings of the prior art, the conditions of the reaction for producing the organic semiconductors can be modified so that the conductivity, type and properties of the polymers obtained are changed, the main factors which can be changed in the course of the reaction , are among others the temperature5 the concentration of the reaction participants \ the state of avidity or basicity and the degree of hydration,

In practice, the best results so far have been obtained with semiconductors based on polyanilines , which are obtained by oxidizing polycondensation reaction of aniline in the presence of alkali persulfates in normal sulfuric acid metal. can be obtained. A polyaniline, which is produced by directed oxidation of 4 moles of aniline per mole of ammonium persulfate and then processed by pressing into a sintered, less porous mass, has an electronic conductivity of 10 "ohms""=a" and an ionic conductivity

-P -1-1
of 3 ° 10 Ohm .cm ₆ The charge carriers are fixed by equilibrating the material in aqueous normal sulfuric acid ο

BAD'ORIGINAL

For the production of an electrochemical power generator with electrodes according to the invention one can 'either two Electrodes made from the same basic organic semiconductor but with the one in each electrode ■ Has different oxidation levels, or combine two electrodes made from different organic semiconductors are made, or an electrode according to the invention together with a conventional one. Use electrode < >

For experimental purposes, electrolysis cells can be used, which consist of a container containing an electrolyte solution and there are two electrodes immersed in the solution =.

cells which have two electrodes according to FIG Invention included, described in more detail *

Each electrode consists of a tube, at the bottom of which At the end a plate made of organic semiconductor material is attached, over which there is a small amount of mercury and two platinum conductors, each in. the Dip mercury into each tube of the cell * -.

In another embodiment, which is more compact than the one described above, the cell contains two vertical glass tubes, the lower open , opposite ends of which are angled and closed with a plug made of semiconductor material! while a membrane impregnated with electrolyte is inserted between these plugs »As with the previous one. In the embodiment, mercury is placed at the bottom of each tube in contact with each plug, and conductors made of platinum are immersed in the mercury of each tube <>

In these two exemplary embodiments, the electrolyte is an aqueous sulfuric acid solutiona

10 9839/0310 ⁸ AO original

The mercury can, of course, be another conductive one Metal can be replaced preferably in the form of a thin plate »In this way it is possible to use dry accumulators build, in which at least one electrolysis cell is used, the membrane soaked with electrolyte contains that of two platelets made of organic semiconductor material are surrounded, the platelets themselves being in contact with thin metal plates =, It is possible a certain number of such cells to interconnect

In a variant, the membranes or tissues that are impregnated with electrolyte, such as normal sulfuric acid, even with solid semiconductor materials, z-J, polyanilines which are applied to the membranes by impregnation or grafting »

When interconnecting such membranes, one half of them, which are combined with polymers, represents the Anode there, while the other half plays the role of cathode plays, ■

Electrochemical cells have been described above in which two symmetrical electrodes are used according to the invention. to build mixed accumulators in which the anodes are made of metals or oxides, hydroxydea or inorganic see non-stoichiometric. Connections that partially Have salt character, can consist, while the cathodes, of organic, polymeric semiconductors of the described ! Byps exist,

The invention is illustrated by the following examples described with cfem images <,

Figo 1 shows schematically an electrode according to the invention

Figo 2 and 3 show two different electrochemical Power generator according to the invention »

bad original

Pig 4 shows a single cell of another electrochemical Generator,

Pig, 5 through 8 are graphs showing the operation of the electrochemical power generator shown in FIG s -illustrate ο

The first examples describe certain methods of manufacture of semiconductor materials used for the purposes of Invention are suitable.

Hjejp ^ osition aS _-1 PpIvanilin £

To a kept at 25 ⁰ C solution of aniline sulfate in lioriaalschwefelsäure containing 40 g of aniline / liter, is added 23 g of ammonium persulfate with vigorous Eühren. After a short time, which can be a few minutes, a black, green reflective polymer precipitates. The suspension is then repeatedly washed with aqueous oleic sulfuric acid and filtered until the aniline has disappeared from the wash water. This requires this treatment to be repeated 4 to 5 times. The product is then subjected to equilibrium in a room with a regulated atmosphere , in which the water vapor partial pressure is kept constant at 6 mm Hg,

The conductivity of this polymer, which was measured on plates produced by pressing the powder under a pressure of 5000 kg / cm *, at 20 ° 0, is C ^ = 0.080 t 0.006 ohms "'ecm *" ¹ . ,

Beaspiel, 2
Manufacture ^ onJPolj ^ lT ^ me t hy! Aniline

To an aqueous solution of N-IIethyl 1-aniline sulfate in normal sulfuric acid, which contains 50 g of H-methyl aniline, is kept ^{at 25 0 G, 23 g of ammonium persulfate are added under vigorous}

109839/0310 BADORiGlNAL

tiger stirring given. After a while, the one Hour, a green polymer is deposited .. '/.

The suspension is then several times alternating with washed aqueous solutions of normal sulfuric acid and filtered until there is no more aniline in the wash water This requires repeating this 4 to 5 times Treatment, the product is then placed in a room with a controlled atmosphere in which the partial pressure of the water vapor is kept constant at 6 mm Hg, "the Subject to equilibrium adjustment =

To the semiconductors which can be used for the purposes of the invention to try out 'measurements of the electronic conductivity carried out with the aid of cells provided with metal electrodes, during the measurements of the ionic conductivity can be made with cells that are electrolytic Electrodes are provided.

The devices described below were Plates used by pressing polyaniline powder of the Svps described in Example 1 or Example 2 "is used

Pig. 1 shows a single electrode according to the invention, for the plates 1 with the following dimensions were used:

Base diameter: 5 mm

Height: 1 to 5 mm

Weight j. - 30 to 100 mg dry matter,

These plates or plugs are made with the help of an adhesive glued to the inside of a glass tube 2 of 6 mm inner diameter that the base of the Cylinder is flush with the end of the glass tube 2. The glass tube 2 can be straight or angled, as in pig. * shown.

09839/03 10.

BAO

Above the stopper 1 there is a small amount of mercury. A platinum wire .4 _{5 of} the. The electrical contact can also be made by printing a metallic collector foil on the back.

The cell of the actual electrochemical .Stromerzeugers is shown for example in Pig = 2 and 3, the cell consists of a container 5 which is an aqueous solution of 6 Kormalschwefelsäure and two electrodes of the in Pig * ^Λ - contains Ty ρs shown. In Pig, 2 ^ these two electrodes contain straight glass tubes, while in Fig. 3 these glass tubes are angled »

In the following description of those in these figures cells shown, one electrode is called the anode and the other is called the cathode *

A variant of the cell for the electrochemical power generator is shown in Pig * 4 = This cell is provided with two glass tubes 12a-12b ", the lower ends of which are angled so that they are opposite one another o A plate Ha-" Ib made of polyaniline is at the end each Eohres 12a-12b attached = an oilulose film 16, which is impregnated with KOrr.al sulfuric acid, is inserted between the two plates 11a-11b. As in the previous examples, the lower part of each Eobres is filled with mercury at 13 = Metal wires _: 14 * especially made of Plstiss, immerse in each of the tubes - 12a- ': 2b _f

In the case of the accumulator shown in Pig, 2, _{v is} the current potential of the electrode immersed in the sulfuric acid, +650 mV against the hydrogen electrode, corresponding to +400 mV against the calomel electrode.

109839/03 1Ö

Accumulation or_s

The cathode immersed in the normal sulfuric acid is all an electrochemical reaction at a potential controlled with a classic polarographic device subject ;, Two equivalent reduction methods can be applied:

In the first method, the electrode is subjected to a potential of 250 mV against the hydrogen electrode 0 mV against the calomel electrode. The curve showing the change in amperage over time, is shown in Fig = 5.

In the second method, the electrode is reduced by successively gradual potentials between -! -. 400 mV against a calomel electrode and 0 mV against a calomel electrode placed on the electrode. The curve that the change of the zero current potential. depending on the during reflects the reduction in the amount of electricity delivered, is shown in FIG. 6. The amount of electricity that for the reduction of the electrode is expended. amounts to -' 30 to 40 Ah / kg, ■ ■ '. -

lh _ri prste _n discharge,, of, accumulator

The in Fig-; 2 shown accumulator, the anode and. The cathode which has been reduced in the above description is connected to a discharge current circuit in which a resistor E "from 500 to 1000 ohms, an ammeter and a voltmeter are connected. The curve that shows the discharge current over time reproduces _t is shown in FIG.

For charging, the connection terminals of the electrodes are included the terminals of a DC power source from. 4 to 500 mV

109839/0310 BADOR ₁ G ₁ NAL

1871737

_ ig -

The charging curve of the .Akkumulator is connected in Fig- 8 shown. If the accumulator has been charged, canr it will be discharged under the conditions described above

In general, in the case of the accumulator shown in FIG. 2, the experimentally determined charge or discharge capacity is 15 to 20 Ah / kg electrode, this corresponds to a usable energy of 3 to 4 watt hours / kg electrode,

ÖÄD ORIGINAL 109839/0310

Claims (8)

Claims Electrode for electrochemical power generators, characterized in that it contains at least one macromolecular organic semiconductor with both electronic and ionic conductivity in solid form, which is inserted between a metallic conductor and an aqueous electrolytic medium _e 2.) Electrode according to claim 1, characterized in that one sees an organic semiconductor with an electronic one Conductivity greater than 10 ~ ohms \ cm ~ in Compound with an ionic conductivity greater than 10 ohms. cm used. 3.) Electrode according to claim 1 and 2, characterized in that that an organic semiconductor with an -electronic- -2 -! 2 ■ see conductivity in the range between 10 and 10 - 1 - "1 Ohm ~ .cm ~ used. 4.) Electrode according to claim 1 to 3, characterized in that one uses an aqueous electrolytic medium with a stabilized p "- \\ ^r ert, which with the help of a strongly acidic Xl Substance is fixed in the acidic range and with the help of a strongly basic substance in the basic range. 5. / Electrode according to claim 1 to 4, characterized in that that the oxidation products are used as organic semiconductors of aniline and aromatic amines, of am nitrogen or anilines substituted on the benzene ring or of ir.polynuclear, optionally substituted amines. 6.) Electrode according to claim 1 to 4, characterized in that that the macromolecular products obtained are used as organic semiconductors BAO by reacting hydroquinones with anhydrides of aromatic acids _Ä . by polycondensation of resorcinol with an aromatic acid dianhydride or of hydroquinone with phthalic anhydride and pyromellitic anhydrideV by polycondensation of hydrazine with a bicarbonyl derivative, ■. by polycondensation of an aromatic amine with a quinone * by condensation of chloranil with an aromatic bianiin, - '. by pyrolysis of TetraIodpyrröl, Trijodiinidazol and Tetraiodimidazolj, - or by reacting benzidine with 2-amino-8-naphthol- -6-sulfonic acid ο. 7.) Electrode according to claim 1 to 6, characterized in that that the aqueous electroiyrische medium enclosed in a porous structure or in a gel-forming substance. sen is., -. 8.) Electrode according to claim 1 to 6 _S , characterized in that the aqueous electrolytic medium is enclosed in ion exchange membranes = ■ 9 «) Electrode according to claim 1 to 8, characterized in that that one uses the organic semiconductor as granulate * IQ.) Electrochemical current generator ₄ characterized by electrodes made of the same organic semiconductor> which, however, is present in different oxidation stages in each electrode. BATH ORIGINAL »Ί Electrochemical power generator, characterized by the combination of electrodes from different or ^ ji see semiconductors. ^: -X 12,) Electrochemical power generator , characterized by the combination of an electrode according to claims 1 to 9 together with a conventional electrode. 109839/0310 Blank page S ₁ f- ■ *