Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same

Abstract

A nonaqueous electrolyte solution for a secondary battery that inhibits increases in resistance during high-temperature storage in a charged state and decreases in capacity, as well as a secondary battery that uses this lithium nonaqueous electrolyte solution. A lithium nonaqueous electrolyte secondary battery that incorporates this non-aqeuous electrolyte solution and that demonstrates a favorable overall balance of battery performance with respect to performance such as durability, capacity, resistance and output characteristics.

1 . A nonaqueous electrolyte solution comprising:
 an electrolyte, and   a nonaqueous solvent,   wherein the nonaqueous electrolyte solution contains a compound represented by general formula (A), and   (1) at least one compound selected from the group consisting of a nitrile compound, an isocyanate compound, a difluorophosphate, a fluorosulfonate, a lithium bis(fluorosulfonyl)imide, and a compound represented by the following general formula (B), or   (2) a cyclic carbonate compound having a fluorine atom in an amount of 0.01% by mass to 50.0% by mass based on the total amount of the nonaqueous electrolyte solution;   wherein formula (A) is:   
       
         
           
           
               
               
           
         
         wherein R 1  to R 3  represent optionally substituted organic groups having 1 to 20 carbon atoms; and 
         wherein formula (B) is: 
       
       
         
           
           
               
               
           
         
         wherein R 4 , R 5  and R 6  respectively and independently represent an alkyl group, alkenyl group or alkynyl group having 1 to 12 carbon atoms that may be substituted with a halogen atom, and n represents an integer of 0 to 6. 
       
     
     
         2 . A nonaqueous electrolyte solution containing an electrolyte and a nonaqueous solvent, wherein the nonaqueous electrolyte solution contains a compound represented by general formula (1): 
       
         
           
           
               
               
           
         
         wherein X 1  and X 2  independently represent NR 8 , NR 8 R 9  or CR 8 R 9 , to R 9  respectively and independently represent a hydrogen atom, fluorine atom, alkyl group, alkenyl group, alkynyl group or aryl group, and at least one of R 7  to R 9  represents a group having a cyano group, and may be mutually the same or different. 
       
     
     
         3 . The nonaqueous electrolyte solution according to  claim 1 , wherein, in formula (A), at least one of R 1  to R 3  is a hydrocarbon group having a carbon-carbon unsaturated bond. 
     
     
         4 . The nonaqueous electrolyte solution according to  claim 1 , wherein the hydrocarbon group having a carbon-carbon unsaturated bond is an allyl group or a methallyl group. 
     
     
         5 . The nonaqueous electrolyte solution according to  claim 1 , wherein the added amount of the compound containing a structure represented by the general formula (A) is 0.01% by mass to 10.0% by mass based on the total amount of the nonaqueous electrolyte solution. 
     
     
         6 . The nonaqueous electrolyte solution according to  claim 1 , wherein the nitrile compound, the isocyanate compound, the difluorophosphate, the fluorosulfonate, the lithium bis(fluorosulfonyl)imide and the compound represented by the general formula (B) are contained in an amount of 0.01% by mass to 10.0% by mass based on the total amount of the nonaqueous electrolyte solution. 
     
     
         7 . The nonaqueous electrolyte solution according to  claim 1 , wherein the cyclic carbonate having a fluorine atom is at least one compound selected from the group consisting of monofluoroethylene carbonate, 4,4-difluoroethylene carbonate and 4,5-difluoroethylene carbonate. 
     
     
         8 . The nonaqueous electrolyte solution according to  claim 1 , wherein the nonaqueous electrolyte solution contains at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond, an acid anhydride, a vinyl sulfonate ester, an aromatic compound having 12 carbon atoms or less and a linear carboxylate ester. 
     
     
         9 . The nonaqueous electrolyte solution according to  claim 2 , wherein the compound represented by the general formula (1) comprises any one of formulas (2) to (9): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         10 . The nonaqueous electrolyte solution according to  claim 2 , wherein the content of the compound represented by the general formula (1) is a ratio of 0.001% by mass to 10% by mass based on the total of the nonaqueous electrolyte solution. 
     
     
         11 . The nonaqueous electrolyte solution according to  claim 2 , which contains at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond, a cyclic carbonate having a halogen atom, a monofluorophosphate, a difluorophosphate and a nitrile compound. 
     
     
         12 . A nonaqueous electrolyte secondary battery comprising:
 a positive electrode capable of occluding and releasing lithium ions,   a negative electrode capable of occluding and releasing lithium ions, and   the nonaqueous electrolyte solution according to  claim 1 .   
     
     
         13 . The nonaqueous electrolyte secondary battery according to  claim 12 , wherein the negative electrode active material of the negative electrode capable of occluding and releasing lithium ions has carbon as a constituent element thereof. 
     
     
         14 . The nonaqueous electrolyte secondary battery according to  claim 13 , wherein the negative electrode active material of the negative electrode capable of occluding and releasing lithium ions has silicon (Si) or tin (Sn) as a constituent element thereof. 
     
     
         15 . The nonaqueous electrolyte secondary battery according to  claim 14 , wherein the negative electrode active material of the negative electrode capable of occluding and releasing lithium ions is a mixture or complex of particles having silicon (Si) or tin (Sn) as a constituent element thereof and graphite particles. 
     
     
         16 . The nonaqueous electrolyte secondary battery according to  claim 15 , wherein the content of the particles having silicon (Si) or tin (Sn) as a constituent element thereof based on the total of the particles having silicon (Si) or tin (Sn) as a constituent element thereof and the graphite particles is 0.1% by mass to 25% by mass. 
     
     
         17 . A nonaqueous electrolyte secondary battery provided with a positive electrode capable of occluding and releasing lithium ions and a negative electrode capable of occluding and releasing lithium ions, wherein the nonaqueous electrolyte solution is the nonaqueous electrolyte solution according to  claim 2 . 
     
     
         18 . The nonaqueous electrolyte secondary battery according to  claim 17 , wherein a negative electrode active material of the negative electrode capable of occluding and releasing lithium ions has carbon as a constituent element thereof. 
     
     
         19 . The nonaqueous electrolyte secondary battery according to  claim 18 , wherein a negative electrode active material of the negative electrode capable of occluding and releasing lithium ions has silicon (Si) or tin (Sn) as a constituent element thereof. 
     
     
         20 . The nonaqueous electrolyte secondary battery according to  claim 19 , wherein a negative electrode active material of the negative electrode capable of occluding and releasing lithium ions is a mixture or complex of particles having silicon (Si) or tin (Sn) as a constituent element thereof and graphite particles.