Secondary battery or cell with improved rechargeability

Abstract

A secondary battery or cell with improved rechargeability is obtained by combination of (A) a cathode active material comprising a chalcogen compound of a transition metal, (B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt and (C) an anode active material comprising lithium metal in electrical contact with an electrically conductive carbonaceous material which is a pyrolysis residue of an organic material such as synthetic high polymers. The anode active material can be formed in situ within the battery, by self discharge of lithium metal into the carbonaceous material. The battery or cell is of excellent properties, such as stability or flatness of discharge voltage and electric capacity.

What is claimed as new and desired to be secured by Letters Patent is: 
     
       1. A secondary battery or cell with improved rechargeability, which comprises: (A) a cathode active material comprising a chalcogen compound of a transition metal,   (B) an electrolyte comprising a organic solvent having dissolved therein a lithium salt, and   (C) an anode active material comprising lithium metal in electrical contact with an electrically conductive substantially amorphous carbonaceous material having a conductivity of at least 10 -5  mho/cm and a density of at most 1.8 g/cm 3 ,   said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to 1500° C.,   wherein said anode material is formed in situ within the secondary battery or cell, by self discharge of lithium metal into said carbonaceous material.   
     
     
       2. The secondary battery or cell of claim 1, wherein said organic material is at least one synthetic high polymer selected from the group consisting of polyacrylonitrile, polyvinyl chloride, polyvinylidene choride, polyvinyl alcohol, polybutadiene, polyethylene, polymethyl vinyl ketone, polyphenylene, polystyrene, polyacetylenes, polyarylacetylenes, polyimides, polyamides, polybenzimidazoles, polysemicarbazides, polybenzoxadinones, epoxy resins, furan resins and phenolic resins. 
     
     
       3. The secondary battery or cell of claim 1, wherein said organic material is at least one synthetic high polymer selected from the group consisting of polyarylacetylenes and phenolic resins. 
     
     
       4. The secondary battery or cell of claim 1, wherein said organic material is at least one synthetic high polymer selected from the group consisting of polyarylacetylenes having repeating units of the general formula: ##STR3## wherein X is Cl or methyl, and Y is H, Cl or methyl. 
     
     
       5. The secondary battery or cell of claim 1, wherein said pyrolysis residue is formed by heating the organic material in an inert atmosphere to a temperature sufficiently high to bring about substantially complete thermal decomposition of noncarbon constituents of the organic material. 
     
     
       6. The secondary battery or cell of claim 1, wherein said carbonaceous material is an activated pyrolysis residue of the organic material. 
     
     
       7. The secondary battery or cell of claim 1, wherein said pyrolysis residue is activated by steam activation, drug activation, or partial oxidation. 
     
     
       8. The secondary battery or cell of claim 1, wherein said pyrolysis residue is in the form of film, fiber, fabric, thin plate or powder. 
     
     
       9. The secondary battery or cell of claim 1, wherein the transition metal is selected from the group consisting of metals of Groups IB-VII and Group VIII of the long form periodic table. 
     
     
       10. The secondary battery or cell of claim 1, wherein said chalogen compound is a chalcogenide of at least one transition metal selected from the group consisting of titanium, vanadium, chromium, manganese, cobalt, copper, iron, niobium and molybdenum. 
     
     
       11. The secondary battery or cell of claim 1, wherein said organic solvent is at least one selected from the group consisting of esters, ethers, ketones, aldehydes, nitriles and amides. 
     
     
       12. The secondary battery or cell of claim 1, wherein the lithium salt is selected from the group consisting of LiClO 4 , LiPF 6 , lithium trifluoromethane sulfonate, LiCl, LiBr, LiI, LiAsF 6 , LiBF 4 , LiBCl 4  and LiAlCl 4 . 
     
     
       13. The secondary battery or cell of claim 1, which comprises: (1) a cathode container with an opening,   (2) a first metal net for collecting electricity situated on an inner surface of said container,   (3) said cathode active material (A) placed on top of said first metal net,   (4) a separator containing said electrolyte (B) placed on top of said cathode active material,   (5) a gasket placed so as to maintain the position of the previously recited elements,   (6) said carbonaceous material placed on top of said separator, in electrical contact with   (7) said lithium metal as anode active material (C),   (8) a second metal net for collecting electricity situated on top of said carbonaceous material, and   (9) an anode container having said anode active material situated onto an inner surface, placed into the opening of said cathode container. .Iadd.   
     
     
       14.  A secondary battery or cell with improved rechargeability, which comprises: (A) a cathode active material comprising a chalogen compound of a transition metal,   (B) an electrolyte comprising a organic solvent having dissolved therein a lithium salt, and   (C) an anode active material comprising lithium metal in electrical contact with an electrically conductive substantially amorphous carbonaceous material having a conductivity of at least 10 -5  mho/cm,   said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to 1500° C.,   wherein said anode material is formed in situ within the secondary battery or cell, by self discharge of lithium metal into said carbonaceous material. .Iaddend. .Iadd.15. The secondary battery or cell of claim 14, which comprises:   (1) a cathode container with an opening,   (2) a first metal net for collecting electricity situated on an inner surface of said container,   (3) said cathode active material (A) placed on top of said first metal net,   (4) a separator containing said electrolyte (B) placed on top of said cathode active material,   (5) a gasket placed so as to maintain the position of the previously recited elements,   (6) said carbonaceous material placed on top of said separator, in electrical contact with   (7) said lithium metal as anode active material (C),   (8) a second metal net for collecting electricity situated on top of said carbonaceous material, and   (9) an anode container having said anode active material situated onto an inner surface, placed into the opening of said cathode container.   
     
     
        .Iaddend. .Iadd.16.  A secondary battery or cell with improved rechargeability, which comprises: (A) a cathode active material comprising a chalcogen compound of a transition metal,   (B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt, and   (C) an anode comprising an electrically conductive substantially amorphous carbonaceous material having a conductivity of at least 10 -5  mho/cm containing lithium therein, said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to about 1500° C.,   wherein said lithium is intercalated into said carbonaceous material upon charging the cell and said lithium is deintercalated from said carbonaceous material upon discharging the cell. .Iaddend. .Iadd.17. The secondary battery or cell of claim 14, wherein said carbonaceous material has a density of at most 1.8 g/cm 3 , the density being a bulk density. .Iaddend. .Iadd.18. A secondary battery or cell with improved rechargeability, which comprises:   (A) a cathode active material comprising a chalcogen compound of a transition metal,   (B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt, and   (C) an anode comprising an electrically conductive carbonaceous material having a conductivity of at least 10 -5  mho/cm containing lithium therein, said carbonaceous material being substantially free from an X-ray diffraction characteristic of graphite, said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to about 1500° C.,   wherein electromotive reactions proceed at the anode side according to the following equations: ##STR4##