Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using same

Abstract

The present invention relates to a nonaqueous electrolytic solution for use in a nonaqueous electrolytic solution secondary battery that comprises a negative electrode and a positive electrode capable of storing and releasing metal ions, and a nonaqueous electrolytic solution, wherein the nonaqueous electrolytic solution contains the specific compounds (A) and (B).

1 . A nonaqueous electrolytic solution, comprising:
 (A) a compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond; and   (B) at least one compound selected from the group consisting of a carbonate ester having an unsaturated bond, a compound represented by the following general formula (1), a compound having a S═O group, monofluorophosphate, difluorophosphate, fluorosulfonate, and an imide salt,   
       
         
           
           
               
               
           
         
         wherein M represents a transition metal, an element of group 13, 14, or 15 of the periodic table, or a hydrocarbon group of 1 to 6 carbon atoms that may have a heteroatom, where when M represents a transition metal, or an element of group 13, 14, or 15 of the periodic table, Z a+  is a metal ion, a proton, or an onium ion, a represents 1 to 3, b represents 1 to 3, 1 represents b/a, m represents 1 to 4, n represents 1 to 8, t represents 0 to 1, p represents 0 to 3, q represents 0 to 2, and r represents 0 to 2, and where when M is a hydrocarbon group of 1 to 6 carbon atoms that may have a heteroatom, Z a+  does not exist, and a=b=1=n=0, m=1, t represents 0 to 1, p represents 0 to 3, q represents 0 to 2, and r represents 0 to 2, 
         R 1  represents a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms that may have a heteroatom, or X 3 R 4  where R 1  that exists in number n may bind to one another to form a ring, R 2  represents a direct bond, or a hydrocarbon group of 1 to 6 carbon atoms that may have a heteroatom, X 1 , X 2 , and X 3  each independently represents O, S, or NR 5 , and R 3 , R 4 , and R 5  each independently represent hydrogen, a hydrocarbon group of 1 to 10 carbon atoms that may have a heteroatom, where a plurality of R 3  and R 4  may bind to one another to form a ring, and Y 1  and Y 2  each independently represent C, S, or Si, wherein, when Y 1  or Y 2  is C or Si, q or r is 0 or 1, and, when Y 1  or Y 2  is S, q and r each are 2. 
       
     
     
         2 . The nonaqueous electrolytic solution according to  claim 1 , wherein the compound having a S═O group is a compound represented by the following general formula (2), 
       
         
           
           
               
               
           
         
         wherein L represents an optionally substituted organic group with valence number a, R 4  represents a halogen atom, a hydrocarbon group of 1 to 4 carbon atoms, or an alkoxy group, α is an integer of 1 or more, and, when α is 2 or more, a plurality of R 4  may be the same or different, and wherein R 4  and L may bind to each other to form a ring. 
       
     
     
         3 . The nonaqueous electrolytic solution according to  claim 2 , wherein at least one compound selected from the group consisting of the carbonate ester having an unsaturated bond, the compound represented by the general formula (1), and the compound represented by the general formula (2) is at least one compound selected from the group consisting of vinylene carbonate, vinylethylene carbonate, ethynylethylene carbonate, methylpropargyl carbonate, dipropargyl carbonate, lithium bis(oxalate)borate, lithium difluorooxalateborate, lithium tris(oxalate)phosphate, lithium difluorobis(oxalate)phosphate, lithium tetrafluorooxalatephosphate, ethynylethylene sulfate, and propynyl vinyl sulfonate. 
     
     
         4 . The nonaqueous electrolytic solution according to  claim 1 , wherein at least one compound selected from the group consisting of the monofluorophosphate, the difluorophosphate, the fluorosulfonate, and the imide salt is at least one compound selected from the group consisting of lithium monofluorophosphate, lithium difluorophosphate, lithium fluorosulfonate, LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , and LiN(C 2 F 5 SO 2 ) 2 . 
     
     
         5 . A nonaqueous electrolytic solution secondary battery, comprising:
 a carbon-containing negative electrode;   a positive electrode capable of storing and releasing metal ions; and   a nonaqueous electrolytic solution,
 wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution of  claim 1 .