Oxiranyl ester derivatives as additive for electrolytes in lithium ion batteries

Patent metadata

Field	Value
Publication number	US-9640839-B2
Application number	US-201414907954-A
Country	US
Kind code	B2
Filing date	Jul 11, 2014
Priority date	Jul 23, 2013
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

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.

First claim

The invention claimed is:

1. An electrolyte composition (A) comprising:
(i) an aprotic organic solvent;
(ii) a conducting salt;
(iii) a compound of formula (I)

wherein
R 1 is selected from the group consisting of C(O)C(O)OR 7 , S(O) 2 R 7 , S(O) 2 OR 7 , (CH 2 ) s SO 2 (CH 2 ) t R 7 , P(O)(OR 7 )R 7 , and P(O)(OR 7 ) 2 ;
R 2 is selected from the group consisting of H, F, 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 may be 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 8 , C(O)R 8 , C(O)OR 8 , OC(O)R 8 , OC(O)OR 8 , OC(O)C(O)OR 8 , S(O) 2 OR 8 and OS(O) 2 R 8 ;
R 3 and R 4 are each independently selected from the group consisting of H, F, 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, alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl, may be substituted by one or more substituents selected from the group consisting of F, CN, and optionally fluorinated oxiranyl;
R 5 and R 6 are each 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 may be substituted by one or more substituents selected from the group consisting of F, CN, and optionally fluorinated oxiranyl;
R 7 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 may be substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, OR 9 , OC(O)R 9 , C(O)R 9 , C(O)OR 9 , OC(O)OR 9 , OC(O)C(O)OR 9 , S(O) 2 OR 9 , OS(O) 2 R 9 , and C 3 -C 6 (hetero)cycloalkyl which may be substituted by one or more substituents selected from the group consisting of F, 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 may be substituted by one or more substituents selected from the group consisting of F, CN, and optionally fluorinated oxiranyl;
R 8 and R 9 are each 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 may be substituted by one or more substituents selected from the group consisting of F, CN, and optionally fluorinated oxiranyl;
wherein s and t are independently from each other 1, 2, or 3; and
(iv) optionally a further additive.

2. The electrolyte composition (A) according to claim 1 wherein R 1 is C(O)C(O)OR 7 .

3. The electrolyte composition (A) according to claim 1 wherein R 1 is selected from the group consisting of S(O) 2 R 7 , S(O) 2 OR 7 , (CH 2 ) m SO 2 (CH 2 ) n R 7 , wherein m and n are independently from each other 1, 2, or 3, P(O)(OR 7 )R 7 , and P(O)(OR 7 ) 2 .

4. The electrolyte composition (A) according to claim 1 , wherein the compound of formula (I) comprises at least two oxirane cycles.

5. The electrolyte composition (A) according to claim 1 , wherein R 7 comprises an oxirane cycle.

6. The electrolyte composition (A) according to claim 1 , wherein the compound of formula (I) has a formula (II)

wherein
R 1a is selected from the group consisting of —C(═O)—, —C(═O)O—, —C(═O)C(═O)O—, —C(═O)R 7a C(═O)O—, —S(O) 2 —, —S(O) 2 O—, —(CH 2 ) s SO 2 (CH 2 ) t O—, —P(O)(OR 7b )—, and —P(O)(OR 7b )O—;
R 2 , R 2a , R 3 , R 3a , R 4 , R 4a , R 5 , R 5a , R 6 and R 6a are each independently selected from the group consisting of H, F, 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 may be substituted by one or more substituents selected from the group consisting of F, CN, and optionally fluorinated oxiranyl;
R 7a is selected from the group consisting of C 1 -C 4 alkanediyl, C 2 -C 4 alkenediyl, C 2 -C 4 alkynediyl and 1,2-oxiranediyl;
R 7b 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 may be substituted by one or more substituents selected from the group consisting of F, CN, and optionally fluorinated oxiranyl, and wherein s and t are independently from each other 1, 2, or 3.

7. The electrolyte composition (A) according to claim 1 , wherein the aprotic organic solvent (i) is selected from the group consisting of:
(a) a cyclic or noncyclic organic carbonate, which may be partly halogenated,
(b) a di-C 1 -C 10 -alkylether, which may be partly halogenated,
(c) a di-C 1 -C 4 -alkyl-C 2 -C 6 -alkylene ether or polyether, which may be partly halogenated,
(d) a cyclic ether, which may be partly halogenated,
(e) a cyclic or acyclic acetal or ketal, which may be partly halogenated,
(f) an orthocarboxylic acid ester, which may be partly halogenated,
(g) a cyclic or noncyclic ester of a carboxylic acid, which may be partly halogenated,
(h) a cyclic or noncyclic sulfone, which may be partly halogenated,
(i) a cyclic or noncyclic nitrile or dinitrile, which may be partly halogenated, and
(j) an ionic liquid, which may be partly halogenated.

8. The electrolyte composition (A) according to claim 1 , wherein the conducting 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 in the range from 0 to 6 and y is an integer in the range 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 may be 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 the central B-atom;
LiClO 4 ; LiAsF 6 ; LiCF 3 SO 3 ; Li 2 SiF 6 ; LiSbF 6 ; LiAlC 4 ; Li[N(SO 2 F) 2 ]; lithi

Assignees

• Basf Se

Inventors

• Porta Garcia Marta
• Chesneau Frederick Francois
• Schmidt Michael
• Riedel Dominic
• Schroeder Denis
• Teles Joaquim Henrique
• Garsuch Arnd
• Herzog Stefan
• Kirste Axel
• Krieg Patrick
• Karcher Christian
• Vautravers Nicolas
• Meini Stefano

Classifications

• H01M10/0569

  characterised by the solvents · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• C07D303/12

  with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms · CPC title

• C07D303/16

  by esterified hydroxyl radicals · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title