Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery using the same

Abstract

A non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and a non-aqueous liquid electrolyte, having high charging capacity, capable of maintaining excellent characteristics over a long period of time and excellent in discharge capacity retention in particular, is provided. The non-aqueous liquid electrolyte contains at least one of: (i) a compound represented by the general formula (I) below and a saturated cyclic carbonate compound; (ii) a compound represented by the general formula (II) below; and (iii) a compound represented by the general formula (III-1) below. (In the above formula (I), n represents an integer which is greater than or equal to 3, m represents an integer which is greater than or equal to 1, and the sum of n and m is greater than or equal to 5. All or part of the hydrogen atoms may be substituted with a fluorine atom.) (In the above formula (II), X represents —SO 2 or —SO—, and R 1 to R 6 each represent, independently of each other, an unsubstituted alkyl group or halogen-substituted alkyl group.) A-N═C═O   (III-1) (In the above formula (III-1), A represents an element or group other than a hydrogen.)

1 . A non-aqueous liquid electrolyte to be used for a non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and the non-aqueous liquid electrolyte, the anode electrode containing a anode electrode active material having at least one kind of atom selected from the group consisting of Si atom, Sn atom and Pb atom,
 wherein said non-aqueous liquid electrolyte contains a carbonate having at least either an unsaturated bond or a halogen atom, and also contains at least one of:   (i) a compound represented by the general formula (I) below and a saturated cyclic carbonate compound;   (ii) a compound represented by the general formula (II) below; and   (iii) a compound represented by the general formula (III-1) below.   
       
         
           
           
               
               
           
         
       
       (In the above formula (I), n represents an integer which is greater than or equal to 3, m represents an integer which is greater than or equal to 1, and the sum of n and m is greater than or equal to 5. All or part of the hydrogen atoms may be substituted with a fluorine atom.) 
       
         
           
           
               
               
           
         
       
       (In the above formula (II), X represents a group represented by 
       
         
           
           
               
               
           
         
       
       and R 1  to R 6  each represent, independently of each other, an unsubstituted alkyl group or halogen-substituted alkyl group.)
   [Chemical Formula 5] 
   A-N═C═O   (III-1) 
 
       (In the above formula (III-1), A represents an element or group other than a hydrogen.) 
     
     
         2 . A non-aqueous liquid electrolyte as defined in  claim 1 , wherein in the above general formula (I), n and m are integers different from each other. 
     
     
         3 . A non-aqueous liquid electrolyte as defined in  claim 1  or  claim 2 , wherein in said non-aqueous liquid electrolyte, the concentration of said compound represented by the general formula (I) is 5 volume % or higher, and 95 volume % or lower. 
     
     
         4 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  3 , wherein in said non-aqueous liquid electrolyte, the concentration of said saturated cyclic carbonate is 5 volume % or higher, and 50 volume % or lower. 
     
     
         5 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  4 , wherein in the above general formula (II), R 1  to R 6  each represent, independently of each other, an unsubstituted or fluorine-substituted alkyl group having 1 to 3 carbon atoms. 
     
     
         6 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  5 , wherein in said non-aqueous liquid electrolyte, the concentration of said compound represented by the general formula (II) is 0.01 weight % or higher, and 10 weight % or lower. 
     
     
         7 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  6 , wherein said compound represented by the general formula (III-1) is a compound selected from the compounds represented by the general formula (III-2) below. 
       
         
           
           
               
               
           
         
       
       (In the above general formula (III-2),
 X 1  and X 2  represent, independently of each other, an element other than hydrogen, 
 Z represents an arbitrary element or group, 
 m and n represent, independently of each other, an integer greater than or equal to 1, and 
 when m is 2 or greater, each of Z may be the same or different from each other.) 
 
     
     
         8 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  7 , wherein said compound represented by the general formula (III-1) is a compound selected from the group represented by the general formula (III-3) below. 
       
         
           
           
               
               
           
         
       
       (In the above general formula (III-3), R represents, independently of each other, an alkyl group or aryl group that may have a substituent. In addition, more than one R may be connected to each other to form a ring.) 
     
     
         9 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  8 , wherein in said non-aqueous liquid electrolyte, the concentration of said compound represented by the general formula (III-1) is 0.01 weight % or higher, and 10 weight % or lower. 
     
     
         10 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  9 , wherein in said non-aqueous liquid electrolyte, the concentration of said carbonate having at least either an unsaturated bond or a halogen atom is 0.01 weight % or higher, and 70 weight % or lower. 
     
     
         11 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  10 , wherein said carbonate having an unsaturated bond or a halogen atom is one or more carbonate compounds selected from the group consisting of vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate and derivatives of these carbonate compounds. 
     
     
         12 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  11 , further comprising ethylene carbonate and/or propylene carbonate. 
     
     
         13 . A non-aqueous liquid electrolyte as defined in any one of  claims 1  to  12 , further comprising at least one additional carbonate selected from the group consisting of dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate and di-n-propyl carbonate. 
     
     
         14 . A non-aqueous liquid electrolyte to be used for a non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and the non-aqueous liquid electrolyte, the anode electrode containing a anode electrode active material having at least one kind of atom selected from the group consisting of Si atom, Sn atom and Pb atom,
 wherein said non-aqueous liquid electrolyte contains a compound represented by the general formula (I) below and a saturated cyclic carbonate compound.   
       
         
           
           
               
               
           
         
       
       (In the above formula (I),
 n represents an integer which is greater than or equal to 3, 
 m represents an integer which is greater than or equal to 1, 
 and the sum of n and m is greater than or equal to 5. 
 All or part of the hydrogen atoms may be substituted with a fluorine atom.) 
 
     
     
         15 . A non-aqueous liquid electrolyte as defined in  claim 14 , wherein in the above general formula (I), n and m are integers different from each other. 
     
     
         16 . A non-aqueous liquid electrolyte as defined in  claim 14  or  claim 15 , wherein in said non-aqueous liquid electrolyte, the concentration of said compound represented by the general formula (I) is 5 volume % or higher, and 95 volume % or lower. 
     
     
         17 . A non-aqueous liquid electrolyte as defined in any one of  claims 14  to  16 , wherein in said non-aqueous liquid electrolyte, the concentration of said saturated cyclic carbonate is 5 volume % or higher, and 50 volume % or lower. 
     
     
         18 . A non-aqueous liquid electrolyte to be used for a non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and the non-aqueous liquid electrolyte, the anode electrode containing a anode electrode active material having at least one kind of atom selected from the group consisting of Si atom, Sn atom and Pb atom,
 wherein said non-aqueous liquid electrolyte contains at least a compound represented by the general formula (II) below.   
       
         
           
           
               
               
           
         
       
       (In the above formula (II),
 X represents a group represented by 
 
       
         
           
           
               
               
           
         
       
       and R 1  to R 6  each represent, independently of each other, an unsubstituted alkyl group or halogen-substituted alkyl group.) 
     
     
         19 . A non-aqueous liquid electrolyte as defined in  claim 18 , wherein in the above general formula (II), R 1  to R 6  each represent, independently of each other, an unsubstituted or fluorine-substituted alkyl group having 1 to 3 carbon atoms. 
     
     
         20 . A non-aqueous liquid electrolyte as defined in  claim 18  or  claim 19 , wherein in said non-aqueous liquid electrolyte, the concentration of said compound represented by the formula (II) is 0.01 weight % or higher, and 10 weight % or lower. 
     
     
         21 . A non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and a non-aqueous liquid electrolyte, the anode electrode containing a anode electrode active material having at least one kind of atom selected from the group consisting of Si atom, Sn atom and Pb atom,
 wherein said non-aqueous liquid electrolyte is a non-aqueous liquid electrolyte defined in any one of  claims 1  to  20 .   
     
     
         22 . A non-aqueous liquid electrolyte to be used for a non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and the non-aqueous liquid electrolyte,
 wherein said non-aqueous liquid electrolyte contains, at least, a carbonate having at least either an unsaturated bond or a halogen atom, and a compound represented by the general formula (III-1) below.
   [Chemical Formula 12] 
   A-N═C═O   (III-1) 
   
       (In the above formula (III-1), A represents an element or group other than a hydrogen.) 
     
     
         23 . A non-aqueous liquid electrolyte as defined in  claim 22  wherein said compound represented by the general formula (III-1) is a compound selected from the group represented by the general formula (III-2) below. 
       
         
           
           
               
               
           
         
       
       (In the above general formula (III-2),
 X 1  and X 2  represent, independently of each other, an element other than hydrogen, 
 Z represents an arbitrary element or group, 
 m and n represent, independently of each other, an integer greater than or equal to 1, and 
 when m is 2 or greater, each of Z may be the same or different from each other.) 
 
     
     
         24 . A non-aqueous liquid electrolyte as defined in  claims 22  or  claim 23 , wherein said compound represented by the general formula (III-1) is a compound selected from the group represented by the general formula (III-3) below. 
       
         
           
           
               
               
           
         
       
       (In the above general formula (III-3), R represents, independently of each other, an alkyl group or aryl group that may have a substituent. In addition, more than one R may be connected to each other to form a ring.) 
     
     
         25 . A non-aqueous liquid electrolyte as defined in any one of  claims 22  to  24 , wherein in said non-aqueous liquid electrolyte, the concentration of said compound represented by the general formula (III-1) is 0.01 weight % or higher, and 10 weight % or lower. 
     
     
         26 . A non-aqueous liquid electrolyte secondary battery comprising a anode electrode and a cathode electrode, capable of intercalating and deintercalating lithium ions, and a non-aqueous liquid electrolyte,
 wherein said non-aqueous liquid electrolyte is a non-aqueous liquid electrolyte defined in any one of  claims 22  to  25 .