Secondary battery

Abstract

This invention provides a secondary battery in a nonaqueous type using a substance indicated in I below and/or a substance indicated in II below as an active material for either of positive and negative electrodes: I: a composite oxide possessing a layer structure and represented by the general formula: A.sub.x M.sub.y N.sub.2 O.sub.2 wherein A stands for at least one alkali metal, M for a transition metal, N for at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z respectively for the number falling in a specific range, II: an n-doped carbonaceous material which has a BET-method specific surface area, and a crystal thickness, Lc, in the X-ray diffraction and a true density, ρ, both having the values falling in a specific range. The secondary battery of this invention is small and light, excels in cyclicity and self-discharging property, and possesses a high energy density.

What is claimed is: .[.1. A secondary battery comprising positive and negative electrodes, a separator, and a nonaqueous electrolyte, wherein said secondary battery is characterized by having as an active material for either of said positive and negative electrodes: 
     
        1.70<ρ<2.18 and 10<Lc<120ρ-189..]. 2. A secondary battery according to claim .[.1.]. .Iadd.21.Iaddend., wherein .[.said.]. A is at least one member selected from the group consisting of lithium, sodium, 
     
     
        and potassium. 3. A secondary battery according to claim .[.1.]. .Iadd.21.Iaddend., wherein .[.said.]. M is at least one member selected 
     
     
        from the group consisting of Ni and Co. 4. A secondary battery according 
     
     
        to claim .[.1.]. .Iadd.21.Iaddend., wherein .[.said.]. N is Sn. .[.5.  A secondary battery according to claim 1, wherein the carbonaceous material is carbon fibers of the vapor-phase growth method and/or the comminuted product thereof.Θ .[.6. A secondary battery according to claim 1, wherein the carbonaceous material is a fired carbonization product of pitch..]. .[.7. A secondary battery according to claim 1, wherein the carbonaceous material is a fired carbonization product of a polymer of acrylonitrile..]. .[.8. A secondary battery according to claim 1, wherein the carbonaceous material is needle coke..]. .[.9. A secondary battery according to claim 1, wherein the active material is formed by using an organic polymer dissolved and/or dispersed in a solvent as a binder..]. .[.10. A secondary battery according to claim 9, wherein the organic polymer has a specific dielectric constant greater than 4.5 at 25° C. and 1 KHz of frequency..]. .[.11. A secondary battery according to claim 9, wherein the organic polymer is at least one polymer or copolymer selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl fluoride, and vinylidene fluoride..]. .[.12. A secondary battery according to claim 1, wherein the separator is a polyolefin type microporous membrane..]. .[.13. A secondary battery according to claim 1, wherein cyclic carbonate is used as a solvent for the nonaqueous electrolyte..]. .[.14. A secondary battery according to claim 13, wherein the cyclic carbonate is at least one member selected from the group consisting of propylene carbonate, ethylene carbonate, and vinylene carbonate..]. .[.15. A secondary battery according to claim 1, wherein either of the positive and negative electrodes includes carbon as a conductor aid in concentration of 1 to 30 parts by weight based on 100 parts by weight of the composite oxide as the active material..]. .[.16. A secondary battery according to claim 15, wherein the carbon is at least one member selected from the group consisting of graphite and carbon 
     
     
        black..]. .[.17.  A secondary battery according to claim 15, wherein the carbon is a mixture of carbon having an average particle diameter of 0.1-10μ and carbon having an average particle diameter of 0.01-0.08μ..]. .[.18. A secondary battery according to claim 1, wherein the positive electrode is a composite oxide possessing a layer structure and represented to the general formula:   A.sub.x M.sub.y N.sub.z O.sub.2        wherein A is at least one member selected from the group consisting of alkali metals, M is a transition metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expression, 0.05≦x≦1.10, 0.85≦y≦1.00, and 0.001≦z≦0.10, respectively..]. .[.19. A secondary battery according to claim 1, wherein the negative electrode is   an n-doped carbonaceous material which has a BET-method specific surface area, A (m 2  /g), being in the range of 0.1<A<100 and a crystal thickness, Lc (Å), based on X-ray diffraction and a true density, ρ (g/cm 3 ), satisfying the conditions, 1.70<ρ<2.18 and 10<Lc<120ρ-189..]. .[.20. A secondary battery according to claim 1, wherein the positive electrode is   a composite oxide possessing a layer structure and represented by the general formula:   A.sub.x M.sub.y N.sub.z O.sub.2        wherein A is at least one member selected from the group consisting of alkali metal, M is a transition metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expressions, 0.05≦x≦1.10, 0.85<y≦1.00, and 0.001≦2≦0.10, respectively and, the negative electrode is   n-doped carbonaceous material which has a BET-method specific surface area, A (m 2  /g), being in the range of 0.1<A<100 and a crystal thickness, Lc (Å), based on X-ray diffraction and a true density, ρ (g/cm 3 ), satisfying the conditions, 1.70<ρ<2.18 and   
     
     
        10<Lc<120ρ-189..]. .Iadd.21.  A secondary battery comprising positive and negative electrodes, a separator, and a nonaqueous electrolyte, wherein said secondary battery is characterized by having as an active material for said positive electrode, (I) a composite oxide possessing a layer structure and represented by the general formula:   A.sub.x M.sub.y N.sub.z O.sub.2     wherein A is at least one member selected from the group consisting of alkali metals, M is a transition, metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expression, 0.05≦x≦1.10, 0.85≦y≦1.00, and   
     
     
        0.001≦z≦0.10, respectively. .Iaddend. .Iadd.22.  A secondary battery comprising a positive electrode, a negative electrode, a separator and a nonaqueous electrolyte, wherein said negative electrode comprises as an active material, a carbonaceous material having the following characteristics: (a) a BET-method specific surface area, A(m 2  /g), being in the range of 0.1<A≦9.1, (b) the relation between crystal thickness, Lc (Å), based on x-ray diffraction and true density, ρ (g/cm 3 ), satisfying the conditions: 1.80<ρ<2.18, 15<Lc<120ρ-189 and Lc>120ρ-227 and (c) a utilization coefficient of at least 0.08 defined by the following formula: ##EQU3##.Iaddend. wherein W stands for the weight of the carbonaceous material used, in grams, the utilization coefficient being defined as the proportion of electrons (or paired cations) reversibly released per carbon     
     
     
        atom of said carbonaceous material.  .Iadd.23.  A secondary battery comprising a positive electrode, a negative electrode, a separator and a nonaqueous electrolyte, wherein said negative electrode comprises, as an active material, a carbonaceous material having the following characteristics: (a) a BET-method specific surface area, A(m 2  /g), being in the range of 0.1<A≦9.1, (b) the relation between crystal thickness, Lc(Å), based on X-ray diffraction and true density, ρ(g/cm 3 ), satisfying the conditions: 1.80<ρ<2.16, 15<Lc<120ρ-196 and Lc>120ρ-227, and (c) a utilization coefficient of at least 0.08 defined by the following formula: ##EQU4##.Iaddend.  wherein W stands for the weight of the carbonaceous material used, in grams, the utilization coefficient being defined as the proportion of electrons (or paired cations) reversibly released per carbon     
     
     
        atom of said carbonaceous material.  .Iadd.24.  A secondary battery according to claim 22 or claim 23, wherein said positive electrode comprises, as an active material, a composite oxide possessing a layer structure and represented by the general formula:   A.sub.x M.sub.y N.sub.z O.sub.2     wherein A is at least one member selected from the group consisting of alkali metals, M is a transition metal, N is at least one member selected from the group consisting of Al, In, and Sn, and x, y, and z satisfy the expressions, 0.05≦x≦1.10, 0.85≦y≦1.00, and 0.001≦z≦0.10, respectively. .Iaddend. .Iadd.25. A secondary battery according to claim 22 or claim 23, wherein the active material of the positive electrode is at least one member selected from the group consisting of Li.sub.(1-x) MnO 2 , Li.sub.(1-x) CoO 2 , Li.sub.(1-x) NiO 2 , V 2  O 5 , and V 6  O 13 . .Iaddend. .Iadd.26. A secondary battery according to claim 22, wherein the carbonaceous material is carbon fibers of the vapor-phase growth method and/or the comminuted   
     
     
        product thereof. .Iaddend. .Iadd.27.  A secondary battery according to claim 22, wherein the carbonaceous material is a fired carbonization product of pitch. .Iaddend. .Iadd.28. A secondary battery according to claim 22, wherein the carbonaceous material is needle coke. .Iaddend. .Iadd.29. A secondary battery according to claim 22, wherein the active material for the negative electrode is applied by using an organic polymer dissolved and/or dispersed in a solvent as a binder. .Iaddend. .Iadd.30. A secondary battery according to claim 29, wherein the organic polymer has a specific dielectric constant greater than 4.5 at 25° C. and 1 KHz of frequency. .Iaddend. .Iadd.31. A secondary battery according to claim 29, wherein the organic polymer is at least one polymer or copolymer selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl fluoride, and vinylidene fluoride. .Iaddend. .Iadd.32. A secondary battery according to claim 22, wherein the separator is a polyolefin 
     
     
        microporous membrane. .Iaddend. .Iadd.33.  A secondary battery according to claim 22 wherein a cyclic carbonate is used as a solvent for the nonaqueous electrolyte. .Iaddend. .Iadd.34. A secondary battery according to claim 33, wherein the cyclic carbonate is at least one member selected from the group consisting of propylene carbonate, ethylene carbonate, and vinylene carbonate. .Iaddend. .Iadd.35. A secondary battery according to claim 22, wherein the positive electrode includes carbon as a conductor aid in a concentration of 1 to 30 parts by weight based on 100 parts by weight of the positive electrode active material. .Iaddend. .Iadd.36. A secondary battery according to claim 35, wherein the carbon is at least one member selected from the group consisting of graphite and carbon black. .Iaddend. .Iadd.37. A secondary battery according to claim 36, wherein the carbon is a mixture of carbon having an average particle diameter of 0.01-10μ and carbon having an average particle diameter of 0.01-0.08μ. .Iaddend.