New electrode materials derived from polyquinonic ionic compounds and their use in electrochemical generators

Abstract

The present invention is concerned with novel compounds derived from polyquinonic ionic compounds and their use in electrochemical generators.

What is claimed is:  
     
         1 . A redox compound having at least one state of oxidation state represented by the general formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 M +  represents an alkaline metallic cation, an alkaline-earth cation, a transition metal cation, a rare earth cation, an organometallic cation, an organic cation of the “nium” type, a repetitive unit of a cationic oxidized conjugated polymer, or a monomeric or polymeric cation optionally having a redox character;  
 X is oxygen, NCN, or C(CN) 2 ;  
 Z is C—Y or N;  
 Y represents oxygen, sulfur, NCN, —C(CN) 2 , with the proviso that when Y is sulfur and n is ≦4, then X is oxygen;  
 R 1  is absent, O, S, NH, —(C═C) r —, —(W═W) r — wherein W is independently CR 6  or N; r varies between 1 and 12; and R 6  is H, halogen, CN, or C 1-12  alkyl, C 2-12  alkenyl or C 6-14  aryl optionally having one or more substituents oxa, aza or thia; and wherein 2 R 6  groups can be bonded to form a cycle comprising from 3 to 7 members;  
 R 2  and R 3  are the same or different and are absent, a carbonated divalent radical, optionally substituted with aza, oxa or thia;  
 q varies between 0 et p;  
 p varies between 1 and 5;  
 n varies between 1 and 10 4 ; and  
 wherein two of R 1 , R 2  and R 3  can be bonded together to form a cycle comprising 3 to 7 members.  
 
     
     
         2 . A compound according to  claim 1  characterised in that it is: 
 a rhodizonic acid salt;  
 a rufigallic acid salt represented by the formula  
                     
 and its oxidation compounds;  
 an elagic acid salt represented by the formula  
                     
 and its oxidation compounds, wherein the oxygen atoms with a double bond can be replaced with a group NCN or C(CN) 2 ;  
 a polymer of thiocyanic acid or 1-cyano-2-mercaptoacetylene represented by the formula  
                     
 and its oxidation and reduction products, wherein Z═N or C—CN;  
 a polymer containing units derived from keto-pyridine represented by the formula  
                     
 and its oxidation and reduction products;  
 an alternated polymer containing benzoquinone and pyrazine units and their oxidation and reduction products;  
 a salt of 1,2-dimercaptocyclobutenedione (dithiosquarique) acid and its oxidation compounds, represented by formulae  
                     
 and their products of oxidation;  
 a salt of 1,5 dihydropyrimido[5,4d]pyrimidine 2,4,6,8(3H, 7H)tetrone represented by the formula  
                     
 and its oxidation compounds:  
 a salt of a dicarboxylic acid comprising groups linked with conjugated segments corresponding to the formula  
                     
 wherein L is independently CR 5 , N or C—CN, and wherein R 5  is hydrogen, C 1-12 alkyl, C 2-12 alkenyle, C 6-10 aryl, C 6-10 aryl C 1-12 alkyl, C 1-12 alkyl C 6-10 aryl optionally substituted with one or more oxa, aza or thia of from 1 to 30 carbon atoms, and wherein 2 R 5  can form an alphatic cycle, an aromatic cycle or a heterocycle containing from 4 to 8 carbon atoms when both L are CR 5 ;  
 a polyamide derived from a dicarboxylic acid comprising groups linked with conjugated segments, corresponding to the formula  
                     
 wherein L et R 5  are as defined above, and Q is a divalent alkylene, alkenylene, arylene, arylalkylene, alkylearylene of from 1 to 30 carbon atoms optionally containing oxa, aza or thia substituents.  
 
     
     
         3 . Compounds according to  claim 2 , wherein the rhodizonic acid salt is lithium rodizonate, potassium rhodizonate or copper rhodizonate, or their reduction products.  
     
     
         4 . Compounds according to  claim 1 , characterized in they are used as a negative electrode component in electrochemical generators when redox couples are comprised between 0.1 and 2 V vs. Li + /Li o ; or as a positive electrode component in electrochemical generator or as an active or passive electrode in electrochromic devices when redox couples are comprised between 2 et 3.7 V vs. Li + /Li o .  
     
     
         5 . A redox electrode material characterized in that it contains, in whole or in part, a compound according to  claim 1 .  
     
     
         6 . A material according to  claim 5  characterized in that it furthers contains at least one electronic conductor and at least one binder.  
     
     
         7 . A material according to  claim 6  wherein the electronic conductor comprises carbon black or graphite powder, and the binder comprises polytetrafluoroethylene, co- or ter-polymer of ethylene, propylene and a diene.  
     
     
         8 . A material according to  claim 5  characterized in that it can be used as a source of lithium to compensate for the inherent losses caused by the formation of passivation layers by the electrodes.  
     
     
         9 . A material according to  claim 8  characterized in that it comprises derivatives corresponding to the following redox anions:  
       
         
           
           
               
               
           
         
       
     
     
         10 . An electrical energy storage system of the primary or secondary generator-type or super-capacity, comprising an electrolyte, at least one negative electrode and at least one positive electrode comprising a compound according to  claim 1 .  
     
     
         11 . A system according to  claim 10  wherein the alkaline cation is lithium cation.  
     
     
         12 . A system according to  claim 10  characterized in that the negative electrode is metallic lithium or an alloy thereof, optionally in the form of a nanometric dispersion in lithium oxide; double nitrides of lithium and a transition metal; low potential oxides of general formula Li 1+y Ti 2−x/4 O 4  wherein x and y vary between 0 et 1; carbon and carbonated products obtained from the pyrolysis of organic materials.  
     
     
         13 . A system according to  claim 10  wherein the positive electrode comprises a further electrode material compound selected from oxides and sulfides of transition metals.  
     
     
         14 . A system according to  claim 10  wherein the electrolyte comprises a polar-type polymer, a polar solvent, or mixtures thereof, and at least one ionic salt.  
     
     
         15 . A system according to  claim 14  wherein the polar-type polymer is a polyether, a vinylidene fluoride-based homo- or copolymer, an acrylonitrile-based homo- or copolymer, or a methyl methacrylate-based homo- or copolymer.  
     
     
         16 . A system according to  claim 14  wherein the polar solvent comprises acyclic and cyclic carbonates, γ-butyrolactone, monoalkylamides and dialkylamides, tetraalkylsulfamides, dialkylatex ethers of mono-, di-, tri- et tetraethylene glycols and oligomers of weight inferiors to 2000 g/mole, and mixtures thereof.