Nonaqueous electrolyte solution and lithium secondary battery using same

Abstract

A non-aqueous electrolyte solution is provided that realizes a large capacity, exhibits high storage characteristics and cycle characteristics, and is capable of inhibiting gas generation. The non-aqueous electrolyte solution comprises a lithium salt and a non-aqueous solvent, and further comprises: a cyclic carbonate compound having an unsaturated bond in a concentration of 0.01 weight % or higher and 8 weight % or lower; and a compound expressed by general formula (Ia) in a concentration of 0.01 weight % or higher and 5 weight % or lower. (in the formula (Ia), R 11 and R 12 represent, independently of each other, an organic group that is composed of one or more carbon atoms and hydrogen atoms and may optionally contain one or more oxygen atoms but excludes unsaturated bonds, provided that at least either R 11 or R 12 has an ether linkage. The total number of carbon atoms of R 11 and R 12 is between 3 and 18, and the total number of oxygen atoms contained in R 11 and R 12 is between 1 and 6.)

1 . A non-aqueous electrolyte solution comprising:
 a lithium salt;   a non-aqueous solvent;   a cyclic carbonate compound having an unsaturated bond in a concentration of 0.01 weight % to 8 weight %; and   a compound expressed by the following formula (Ia) in a concentration of 0.01 weight % to 5 weight %;   
       
         
           
           
               
               
           
         
         wherein R 11  and R 12  represent, independently of each other, an organic group that contains one or more carbon atoms and hydrogen atoms and may optionally contain one or more oxygen atoms but excludes unsaturated bonds, provided that at least either R 11  or R 12  has an ether linkage and the total number of carbon atoms of R 11  and R 12  is between 3 and 18, and the total number of oxygen atoms contained in R 11  and R 12  is between 1 and 6. 
       
     
     
         2 - 5 . (canceled) 
     
     
         6 . A non-aqueous electrolyte solution comprising:
 a lithium salt;   a non-aqueous solvent;   a cyclic carbonate compound having an unsaturated bond in a concentration of 0.01 weight % to 8 weight %; and   a compound expressed by the following formula (Ic) in a concentration of 0.01 weight % to 5 weight %;
   CF n H (3-n) CH 2 X 3   (Ic)
 
   wherein n represents an integer of 1-3 and X 3  represents a group selected from the group consisting of the following formulae (Ic-1)-(Ic-4)   
       
         
           
           
               
               
           
         
         wherein R 31 -R 34  represent, independently of each other, an alkyl group having 1-20 carbon atoms that may be substituted by a halogen atom, and Y 3  represents a divalent hydrocarbon group having 1-10 carbon atoms that may be substituted by a halogen atom. 
       
     
     
         7 . The non-aqueous electrolyte solution of  claim 6 , wherein in the formula (Ic), X 3  is the formula (Ic-2) wherein Y 3  is a divalent alkylene group having 1-10 carbon atoms that may be substituted by a halogen atom. 
     
     
         8 . The non-aqueous electrolyte solution of  claim 6 , wherein in the formula (Ic) X 3  is the formula (Ic-3). 
     
     
         9 . The non-aqueous electrolyte solution of  claim 6 , wherein in the formula (Ic) X 3  is the formula (Ic-4). 
     
     
         10 . The non-aqueous electrolyte solution of  claim 6 , wherein in the formulae (Ic-1)-(Ic-4) each of R 31 -R 34  is an alkyl group having 1-20 carbon atoms substituted by 1-3 fluorine atoms. 
     
     
         11 - 18 . (canceled) 
     
     
         19 . The non-aqueous electrolyte solution of  claim 1 , wherein the cyclic carbonate compound having an unsaturated bond is a compound or a plurality of compounds selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, vinyl vinylene carbonate and methylene ethylene carbonate. 
     
     
         20 . A lithium secondary battery comprising:
 a non-aqueous electrolyte solution; and   a positive electrode and a negative electrode capable of absorbing and desorbing lithium ions;   wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution of  claim 1 .   
     
     
         21 . The non-aqueous electrolyte solution of  claim 6 , wherein the cyclic carbonate compound having an unsaturated bond is a compound or a plurality of compounds selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, vinyl vinylene carbonate and methylene ethylene carbonate. 
     
     
         22 . A lithium secondary battery comprising:
 a non-aqueous electrolyte solution; and a positive electrode and a negative electrode capable of absorbing and desorbing lithium ions; wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution of  claim 6 .