Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using same

Abstract

A nonaqueous electrolytic solution for use in a nonaqueous electrolytic solution secondary battery that includes a negative electrode and a positive electrode capable of storing and releasing metal ions, and a nonaqueous electrolytic solution, wherein the nonaqueous electrolytic solution includes (A) a first compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond; and (B) a second compound having a S═O group and/or a third compound of formula (1)

1 . A nonaqueous electrolytic solution suitable for use in a nonaqueous electrolytic solution secondary battery including a negative electrode and a positive electrode capable of storing and releasing metal ions, and the nonaqueous electrolytic solution,
 wherein the nonaqueous electrolytic solution comprises:   (A) a first compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond; and   (B) a second compound having a S═O group and/or a third compound of formula (1)   
       
         
           
           
               
               
           
         
         wherein 
         M is a transition metal, an element of group 13, 14, or 15 of the periodic table, or a C1 to C6 hydrocarbon group optionally comprising a heteroatom, where, when M is the transition metal or the element of group 13, 14, or 15 of the periodic table, Z a+  is a metal ion, a proton, or an onium ion, a is in a range of from 1 to 3, b is in a range of from 1 to 3, 1 is b/a, m is in a range of from 1 to 4, n is in a range of from 1 to 8, t is in a range of from 0 to 1, p is in a range of from 0 to 3, q is in a range of from 0 to 2, and r is in a range of from 0 to 2, and where, when M is the C1 to C6 hydrocarbon group, Z a+  is absent, and a, b, 1, and n are 0, m is 1, t is in a range of from 0 to 1, p is in a range of from 0 to 3, q is in a range of from 0 to 2, and r is in a range of from 0 to 2, 
         R 1  is a halogen atom, a C1 to C20 hydrocarbon group optionally comprising a heteroatom, or X 3 R 4 , R 1  being present in number n optionally bind to one another to form a ring, 
         R 2  is a direct bond, or a C1 to C6 hydrocarbon group optionally comprising a heteroatom, 
         X 1 , X 2 , and X 3  are each independently O, S, or NR 5 , 
         R 3 , R 4 , and R 5  are each independently H, a C1 to C10 hydrocarbon group optionally comprising a heteroatom, a plurality of R 3  and R 4  optionally binding to one another to form a ring, and 
         Y 1  and Y 2  are each independently 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 of  claim 1 , wherein the second compound is present and has a formula (2) 
       
         
           
           
               
               
           
         
         wherein 
         L is an optionally substituted organic group with valence number α, 
         R 4  is a halogen atom, a C1 to C4 hydrocarbon group, or an alkoxy group, 
         α is an integer of 1 or more, and, when α is 2 or more, a plurality of R 4  are the same or different, and 
         wherein R 4  and L optionally bind to each other to form a ring. 
       
     
     
         3 . The nonaqueous electrolytic of  claim 1 , wherein the third compound is at least one compound selected from the group consisting of lithium bis(oxalate)borate, lithium difluorooxalateborate, lithium tris(oxalate)phosphate, lithium difluorobis(oxalate)phosphate, ans lithium tetrafluorooxalatephosphate. 
     
     
         4 . The nonaqueous electrolytic of  claim 2 , wherein the second compound is at least one compound selected from the group consisting of ethynylethylene sulfate and propynyl vinyl sulfonate. 
     
     
         5 . The nonaqueous electrolytic solution of  claim 1 , wherein the first compound is a compound of formula (4): 
       
         
           
           
               
               
           
         
         wherein A 1  to A 6  are independently H, a halogen atom, a C1 to C10 hydrocarbon group optionally comprising a heteroatom, or an optionally substituted hydrogen silicide group of 1 to 10 silicon atoms, and 
         wherein A 1  to A 6  optionally bind to one another to form a ring, when none of A 1  to A 6  is an aliphatic substituent having an unsaturated bond. 
       
     
     
         6 . The nonaqueous electrolytic solution of  claim 1 , wherein the first compound is at least one selected from the group consisting of hexamethyldisilane, hexaethyldisilane, 1,2-diphenyltetramethyldisilane, and 1,1,2,2-tetraphenyldisilane. 
     
     
         7 . The nonaqueous electrolytic solution of  claim 1 , comprising the first compound in a range of from 0.01 mass % or more to 10 mass % or less. 
     
     
         8 . A nonaqueous electrolytic solution secondary battery, comprising:
 a carbon-based negative electrode capable of storing and releasing metal ions;   a positive electrode capable of storing and releasing metal ions; and   the nonaqueous electrolytic solution of  claim 1 .