Oxiranyl-acyl derivatives as additives for electrolytes in lithium ion batteries
The present invention relates to an electrolyte composition (A) containing (i) at least one aprotic organic solvent; (ii) at least one conducting salt; (iii) at least one compound of formula (I) and (iv) optionally at least one further additive.
1. An electrolyte composition (A), comprising
(i) an aprotic organic solvent;
(ii) a conducting lithium salt; and
(iii) a compound of formula (I)
wherein
X is either carbon, S(O) or P(OR 8 );
n is 0 or 1;
R 1 is selected from the group consisting of C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 aralkyl, wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 5 , C(O)R 5 , C(O)OR 5 , OC(O)R 5 , OC(O)OR 5 , OC(O)C(O)OR 5 , OS(O) 2 R 5 , and S(O) 2 OR 5 ;
R 2 is selected from the group consisting of H, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 6 -C 13 aralkyl, C(O)R 6 , C(O)OR 6 , and S(O) 2 OR 6 , wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 7 , C(O)R 7 , C(O)OR 7 , OC(O)R 7 , OC(O)OR 7 , OC(O)C(O)OR 7 , OS(O) 2 R 7 , and S(O) 2 OR 7 ;
R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 or C 7 (hetero)aryl, C 6 -C 13 aralkyl, C(O)R 6 , C(O)OR 6 , and S(O) 2 OR 6 , wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 7 , C(O)R 7 , C(O)OR 7 , OC(O)R 7 , OC(O)OR 7 , OC(O)C(O)OR 7 , OS(O) 2 R 7 and S(O) 2 O R 7 ;
or R 2 and R 3 are combined with each other and form together with a C—C single bond of the oxirane cycle a 5 to 7 membered hydrocarbon cycle which is substituted by at least one selected from the group consisting of O and oxiranyl, and/or two adjacent C-atoms of the hydrocarbon carbon cycle form together with an O-atom an additional oxirane cycle;
R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 aralkyl, wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, and oxiranyl; and
(iv) optionally an additive.
2. The electrolyte composition (A) according to claim 1 ,
wherein
R 1 is C 1 -C 6 alkyl;
R 2 and R 3 are independently H or C 1 -C 6 alkyl; and
R 4 is H, C 1 -C 6 alkyl, or C(O)OR 7 .
3. The electrolyte composition (A) according to claim 1 ,
wherein
R 1 is C 1 -C 6 alkyl; and
R 2 , R 3 and R 4 are hydrogen.
4. The electrolyte composition (A) according to claim 1 ,
wherein
X is a carbon; and
n is 1.
5. The electrolyte composition (A) according to claim 1 ,
wherein
X is carbon;
n is 1;
R 1 is C 1 -C 6 alkyl; and
R 2 , R 3 and R 4 are hydrogen.
6. The electrolyte composition (A) according to claim 1 ,
wherein
X is carbon;
n is 1;
R 1 is C 1 -C 6 alkyl;
R 2 and R 3 are hydrogen;
R 4 is C(O)OR 7 ; and
R 7 is C 1 -C 6 alkyl.
7. The electrolyte composition (A) according to claim 1 ,
wherein
X is S(O); and
n is 1.
8. The electrolyte composition (A) according to claim 1 , wherein the compound of formula (I) comprises at least two oxirane cycles.
9. The electrolyte composition (A) according to claim 1 , wherein the aprotic organic solvent (i) is selected from
(a) a cyclic or noncyclic organic carbonate, which is optionally partly halogenated,
(b) a di-C 1 -C 10 -alkylether, which is optionally partly halogenated,
(c) a di-C 1 -C 4 -alkyl-C 2 -C 6 -alkylene ether or polyether, which is optionally partly halogenated,
(d) a cyclic ether, which is optionally partly halogenated,
(e) a cyclic or acyclic acetal or ketal, which is optionally partly halogenated,
(f) an orthocarboxylic acid ester, which is optionally partly halogenated,
(g) a cyclic or noncyclic ester of a carboxylic acid, which is optionally partly halogenated,
(h) a cyclic or noncyclic sulfone, which is optionally partly halogenated,
(i) a cyclic or noncyclic nitrile or dinitrile, which is optionally partly halogenated, and
(j) an ionic liquid, which is optionally partly halogenated.
10. The electrolyte composition (A) according to claim 1 , wherein the conducting lithium salt (ii) is selected from the group consisting of
Li[F 6-x P(C y F 2y+1 ) x ], wherein x is an integer of from 0 to 6 and y is an integer of from 1 to 20;
Li[B(R 9 ) 4 ], Li[B(R 9 ) 2 (OR 10 O)] and Li[B(OR 10 O) 2 ] wherein each R 9 is independently selected from the group consisting of F, Cl, Br, I, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, and C 2 -C 4 alkynyl, wherein alkyl, alkenyl, and alkynyl are each optionally substituted by one or more OR 11 , wherein R 11 is selected from the group consisting of C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 2 -C 6 alkynyl, and
(OR 10 O) is a bivalent group derived from a 1,2- or 1,3-diol, a 1,2- or 1,3-dicarboxlic acid or a 1,2- or 1,3-hydroxycarboxylic acid, wherein the bivalent group forms a 5- or 6-membered cycle via both oxygen atoms with a central B-atom;
LiClO 4 ; LiAsF 6 ; LiCF 3 SO 3 ; Li 2 SiF 6 ; LiSbF 6 ; LiAlCl 4 , Li[N(SO 2 F) 2 ], lithium tetrafluoro (oxalato) phosphate; lithium oxalate; and
a salt of formula Li[Z(C n F 2n+1 SO 2 ) m ], where m and n are defined as follows:
m=1 when Z is oxygen or sulfur,
m=2 when Z is nitrogen or phosphorus,
m=3 when Z is carbon or silicon, and
n is an integer of from 1 to 20.
11. The electrolyte composition (A) according to claim 1 , comprising the additive (iv) which is selected from the group consisting of vinylene carbonate and a derivative thereof, vinyl ethylene carbonate and a derivative thereof, methyl ethylene carbonate and a derivative thereof, lithium (bisoxalato) borate, lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato) phosphate, lithium oxalate, 2-vinyl pyridine, 4-vinyl pyridine, a cyclic exo-methylene carbonate, a sultone, an organic ester of an inorganic acid, an acyclic or a cyclic alkane having a boiling point at 1 bar of at least 36° C., and an aromatic compound, an optionally halogenated cyclic or acyclic sulfonylimide, an optionally halogenated cyclic or acyclic phosphate ester, an optionally halogenated cyclic or acyclic phosphine, an optionally halogenated cyclic or acyclic phosphite, an optionally halogenated cyclic or acyclic phosphazene, an optionally halogenated cyclic or acyclic silylamine, an optionally halogenated cyclic or acyclic halogenated ester, an optionally halogenated cyclic or acyclic amide, an optionally halogenated cyclic or acyclic anhydride, an ionic liquid and an optionally halogenated organic heterocycle.
12. The electrolyte composition (A) according to claim 1 , wherein a concentration of the compound of formula (I) is 0.001 to 10 wt.-% based on a total weight of the electrolyte composition (A).
13. An electrochemical cell, comprising
(A) the electrolyte composition according to claim 1 ,
(B) a cathode comprising a cathode active material, and
(C) an anode comprising an anode active material.
14. The electrochemical cell according to claim 13 , which is a secondary lithium ion battery.
15. The electrolyte composition (A) according to claim 1 , wherein R 2 is selected from the group consisting of C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 6 -C 13 aralkyl, C(O)R 6 , C(O)OR 6 , and S(O) 2 OR 6 , wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 7 , C(O)R 7 , C(O)OR 7 , OC(O)R 7 , OC(O)OR 7 , OC(O)C(O)OR 7 , OS(O) 2 R 7 , and S(O) 2 O R 7 ,
or R 2 and R 3 are combined with each other and form together with a C—C single bond of the oxirane cycle a 5 to 7 membered hydrocarbon cycle which is substituted by at least one selected from the group consisting of 0 and oxiranyl, and/or two adjacent C-atoms of the hydrocarbon carbon cycle form together with an O-atom an additional oxirane cycle.
16. The electrolyte composition (A) according to claim 1 , wherein R 3 and R 4 are independently selected from the group consisting of H, C 2 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 or C 7 (hetero)aryl, C 6 -C 13 aralkyl, C(O)R 6 , C(O)OR 6 , and S(O) 2 OR 6 , wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 7 , C(O)R 7 , C(O)OR 7 , OC(O)R 7 , OC(O)OR 7 , OC(O)C(O)OR 7 , OS(O) 2 R 7 , and S(O) 2 OR 7 ;
or R 2 and R 3 are combined with each other and form together with a C—C single bond of the oxirane cycle a 5 to 7 membered hydrocarbon cycle which is substituted by at least one selected from the group consisting of O and oxiranyl, and/or two adjacent C-atoms of the hydrocarbon carbon cycle form together with an O-atom an additional oxirane cycle.
17. The electrolyte composition (A) according to claim 1 , wherein R 1 is selected from the group consisting of C 1 or C 3 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 aralkyl, wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 5 , C(O)R 5 , C(O)OR 5 , OC(O)R 5 , OC(O)OR 5 , OC(O)C(O)OR 5 , OS(O) 2 R 5 , and S(O) 2 O R 5 .
18. A method for preparing an electrolyte for an electrochemical cell, the method comprising:
introducing a conducting lithium salt and a compound of formula (I)
into the electrolyte as an additive,
wherein
X is carbon, S(O) or P(OR 8 );
n is 0 or 1;
R 1 is selected from the group consisting of C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 aralkyl, wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR S , C(O)R 5 , C(O)OR 5 , OC(O)R 5 , OC(O)OR 5 , OC(O)C(O)OR 5 , OS(O) 2 R 5 , and S(O) 2 OR 5 ;
R 2 is selected from the group consisting of H, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 6 -C 13 aralkyl, C(O)R 6 , C(O)OR 6 , and S(O) 2 OR 6 , wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 7 , C(O)R 7 , C(O)OR 7 , OC(O)R 7 , OC(O)OR 7 , OC(O)C(O)OR 7 , OS(O) 2 R 7 , and S(O) 2 OR 7 ;
R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 or C 7 (hetero)aryl, C 6 -C 13 aralkyl, C(O)R 6 , C(O)OR 6 , and S(O) 2 OR 6 , wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 7 , C(O)R 7 , C(O)OR 7 , OC(O)R 7 , OC(O)OR 7 , OC(O)C(O)OR 7 , OS(O) 2 R 7 and S(O) 2 O R 7 ;
or R 2 and R 3 are combined with each other and form together with a C—C single bond of an oxirane cycle a 5 to 7 membered hydrocarbon cycle which is substituted by at least one group selected from the group consisting of O and oxiranyl, and/or two adjacent C-atoms of the hydrocarbon carbon cycle form together with an O-atom an additional oxirane cycle;
R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 aralkyl, wherein alkyl, (hetero)cycloalkyl, aralkyl, alkenyl, (hetero)cycloalkenyl, alkynyl, and (hetero)aryl are each optionally substituted by one or more substituents selected from the group consisting of F, CN, and oxiranyl.