Non-aqueous secondary battery

Abstract

A non-aqueous secondary battery contains a positive electrode, a negative electrode, a separator and a non-aqueous electrolytic solution. The positive electrode contains a layered structure lithium-containing compound oxide, or a spinel lithium-containing compound oxide containing manganese as an active material. The non-aqueous electrolytic solution contains at least one additive selected from a sulfonic acid anhydride, a sulfonate ester derivative, a cyclic sulfate derivative and a cyclic sulfonate ester derivative, and a vinylene carbonate or a derivative of the vinylene carbonate.

1 . A non-aqueous secondary battery comprising:
 a positive electrode;   a negative electrode;   a separator; and   a non-aqueous electrolytic solution, wherein   the positive electrode comprises a spinel lithium-containing compound oxide containing manganese as an active material,   the non-aqueous electrolytic solution contains at least one additive selected from the group consisting of: a sulfonic acid anhydride expressed by the general formula (1); a sulfonate ester derivative expressed by the general formula (2); a cyclic sulfate derivative expressed by the general formula (3); and a cyclic sulfonate ester derivative expressed by the general formula (4), and a vinylene carbonate or a derivative of the vinylene carbonate, and   a potential of the positive electrode is 4.35V or higher versus a Li reference electrode where the battery is charged up to a designed electric capacity:   
     
       
         
         
             
             
         
       
     
     wherein each of R 1  and R 2  in the general formula (1) represents independently an organic residue having 1-10 of carbon atoms, each of R 3  and R 4  in the general formula (2) represents independently an organic residue having 1-10 of carbon atoms, R 5  in the general formula (3) represents independently hydrogen or an alkyl group having 1-4 of carbon atoms, which can have a fluorinated substituent, n is 0 or 1, and R 6  in the general formula (4) represents independently hydrogen or an alkyl group having 1-4 of carbon atoms, which can have a fluorinated substituent, m is 0, 1 or 2. 
   
   
       2 . The non-aqueous secondary battery according to  claim 1 , wherein the non-aqueous electrolytic solution contains 0.2 to 5 mass % of the vinylene carbonate or the derivative of the vinylene carbonate. 
   
   
       3 . The non-aqueous secondary battery according to  claim 1 , wherein the spinel lithium-containing compound oxide has a structure expressed by the formula of Li y Mn 2 O 4  wherein 0.98<y≦1.1. 
   
   
       4 . The non-aqueous secondary battery according to  claim 1 , wherein the spinel lithium-containing compound oxide has a structure expressed by the formula of Li y Mn 2 O 4  wherein 0.98<y≦1.1, and a part of the Mn elements is substituted with at least one selected from the group consisting of Ge, Zr, Mg, Ni, Al and Co. 
   
   
       5 . The non-aqueous secondary battery according to  claim 1 , wherein the positive electrode contains a lithium cobalt compound oxide or a lithium nickel compound oxide together with the spinel lithium-containing compound oxide. 
   
   
       6 . A non-aqueous secondary battery comprising:
 a positive electrode;   a negative electrode;   a separator; and   a non-aqueous electrolytic solution, wherein   the positive electrode comprises a spinel lithium-containing compound oxide containing manganese as an active material,   the non-aqueous electrolytic solution contains a cyclic sulfonate ester derivative expressed by the general formula (4), and a vinylene carbonate or a derivative of the vinylene carbonate,   a content of the cyclic sulfonate ester derivative in the non-aqueous electrolytic solution is 1 to 3 mass %, and   a content of the vinylene carbonate or the derivative of the vinylene carbonate in the non-aqueous electrolytic solution is 1 to 5 mass %:   
     
       
         
         
             
             
         
       
     
     wherein R 6  in the general formula (4) represents independently hydrogen or an alkyl group having 1-4 of carbon atoms, which can have a fluorinated substituent, m is 0, 1 or 2. 
   
   
       7 . The non-aqueous secondary battery according to  claim 6 , wherein a potential of the positive electrode is 4.35V or higher versus a Li reference electrode where the battery is charged up to a designed electric capacity. 
   
   
       8 . The non-aqueous secondary battery according to  claim 6 , wherein the spinel lithium-containing compound oxide has a structure expressed by the formula of Li y Mn 2 O 4  wherein 0.98<y≦1.1. 
   
   
       9 . The non-aqueous secondary battery according to  claim 6 , wherein the spinel lithium-containing compound oxide has a structure expressed by the formula of Li y Mn 2 O 4  wherein 0.98<y≦1.1, and a part of the Mn elements is substituted with at least one selected from the group consisting of Ge, Zr, Mg, Ni, Al and Co. 
   
   
       10 . The non-aqueous secondary battery according to  claim 6 , wherein the positive electrode contains a lithium cobalt compound oxide or a lithium nickel compound oxide together with the spinel lithium-containing compound oxide. 
   
   
       11 . A method for preparing the non-aqueous secondary battery according to  claim 1 , the method comprising:
 containing, in a battery case, a positive electrode comprising a spinel lithium-containing compound oxide containing manganese as an active material, a negative electrode, a non-aqueous electrolytic solution that contains at least one additive selected from the group consisting of: a sulfonic acid anhydride expressed by the general formula (1); a sulfonate ester derivative expressed by the general formula (2); a cyclic sulfate derivative expressed by the general formula (3); and a cyclic sulfonate ester derivative expressed by the general formula (4), and a vinylene carbonate or a derivative of the vinylene carbonate;   conducting charging before the battery case is sealed tightly; and   sealing the battery tightly after the charging is terminated:   
     
       
         
         
             
             
         
       
     
     wherein each of R 1  and R 2  in the general formula (1) represents independently an organic residue having 1-10 of carbon atoms, each of R 3  and R 4  in the general formula (2) represents independently an organic residue having 1-10 of carbon atoms, R 5  in the general formula (3) represents independently hydrogen or an alkyl group having 1-4 of carbon atoms, which can have a fluorinated substituent, n is 0 or 1, and R 6  in the general formula (4) represents independently hydrogen or an alkyl group having 1-4 of carbon atoms, which can have a fluorinated substituent, m is 0, 1 or 2. 
   
   
       12 . A method for preparing the non-aqueous secondary battery according to  claim 6 , the method comprising:
 containing, in a battery case, a positive electrode comprising a spinel lithium-containing compound oxide containing manganese as an active material, a negative electrode, a non-aqueous electrolytic solution that contains a cyclic sulfonate ester derivative expressed by the general formula (4), and a vinylene carbonate or a derivative of the vinylene carbonate;   conducting charging before the battery case is sealed tightly; and   sealing the battery tightly after the charging is terminated:   
     
       
         
         
             
             
         
       
     
     wherein R 6  in the general formula (4) represents independently hydrogen or an alkyl group having 1-4 of carbon atoms, which can have a fluorinated substituent, m is 0, 1 or 2.