Acrylonitrile derivatives as additive for electrolytes in lithium ion batteries

Patent metadata

Field	Value
Publication number	US-9722280-B2
Application number	US-201414905606-A
Country	US
Kind code	B2
Filing date	Jul 7, 2014
Priority date	Jul 15, 2013
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

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 (NC)(A 1 X 1 )C═C(X 2 A 2 )(CN) wherein X 1 and X 2 are independently from each other selected from N(R′), P(R 1 ), O, and S, and A 1 and A 2 are selected from H or organic substituents; and electrochemical cells containing electrolyte composition (A).

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
X 1 and X 2 are independently from each other selected from the group consisting of N(R 1 ), N═C(R 2 )—, and P(R 1 );
R 1 is selected from the group consisting of H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 7 -C 3 aralkyl, OR 3 , C(O)R 3 , C(NR 3 )R 4 , and C(O)OR 3 , 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, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, S(O) 2 OR 3a , OS(O) 2 R 3a , S(O) 2 R 3a , OR 3a , C(O)R 3a , C(O)OR 3a , NR 3a R 3b , and NC(O)R 3a R 3b ;
R 2 is selected from the group consisting of H, CN, F, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 7 -C 13 aralkyl, S(O) 2 OR 3 , OS(O) 2 R 3 , S(O) 2 R 3 , OR 3 , C(O)R 3 , C(NR 3 )R 4 , C(O)OR 3 , NR 3 R 4 , NC(O)R 3 , P(O)R 3 R 4 , and SiR 3 R 4 R 5 , 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, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, S(O) 2 OR 3a , OS(O) 2 R 3a , S(O) 2 R 3a , OR 3a , C(O)R 3a , C(O)OR 3a , NR 3a R 3b , and NC(O)R 3a R 3b ;
R 3 , R 4 , R 5 , R 3a , and R 3b are independently from each other selected from the group consisting of H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 7 -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, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, S(O) 2 OR 3c , OS(O) 2 R 3c , S(O) 2 R 3c , OR 3c , C(O)R 3c , C(O)OR 3c , NR 3c R 3d , and NC(O)R 3c R 3d ;
R 3c and R 3d are selected independently from each other from the group consisting of H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, and C 5 -C 7 (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and (hetero)aryl may be substituted by one or more substituents selected from the group consisting of F and CN;
A 1 is selected from the group consisting of C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 7 -C 13 aralkyl, OR 6 , C(O)R 6 , C(NR 6 )R 7 and C(O)OR 6 , 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, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, S(O) 2 OR 6a , OS(O) 2 R 6a , S(O) 2 R 6a , OR, C(O)OR 6a , NR 6a R 6b , and NC(O)R 6a R 6b ;
A 2 is selected from the group consisting of H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 7 -C 13 aralkyl, OR 6 , C(O)R 6 , C(NR 6 )R 7 and C(O)OR 6 , 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, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 5 -C 7 (hetero)aryl, S(O) 2 OR 6 , OS(O) 2 R 6a , S(O) 2 R 6a , OR 6a , C(O)OR 6a , NR 6a R 6b , and NC(O)R 6a R 6b with the proviso that in case of X 2 is O or S, A 2 is neither H nor OR 6 ;
R 6 , R 7 , R 6a , and R 6b are independently from each other selected from the group consisting of H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 (hetero)cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 7 -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, C 1 -C 6 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 7 (hetero)aryl, S(O) 2 OR 6c , OS(O) 2 R 6c , S(O) 2 R 6c , OR 6c , C(O)R 6c , C(O)OR 6c , NR 6c R 6d , and NC(O)R 6c R 6d ;
R 6c and R 6d are independently from each other selected from the group consisting of H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, and C 5 -C 7 (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and (hetero)aryl may be substituted by one or more substituents selected from the group consisting of F and CN;
and

(iv) optionally, a further additive.

2. The electrolyte composition (A) according to claim 1 wherein both X 1 and X 2 are independently from each other selected from the group consisting of N(R 1 ) and P(R 1 ).

3. The electrolyte composition (A) according to claim 1 , wherein the compound of formula (I) is selected from the group consisting of compounds of formula (I) wherein X 1 and X 2 are independently from each other selected from the group consisting of N(R 1 ) and N═C(R 2 ).

4. The electrolyte composition (A) according to claim 1 , wherein the compound of formula (I) is selected from the group consisting of compounds of formula (I a) wherein X 1 is N(R 1 ) and X 2 is N═C(R 2 ),

wherein R 8 is selected from the group consisting of H, C 5 -C 7 (hetero)aryl and C 7 -C 13 aralkyl, and R 9 is selected from the group consisting of C 5 -C 7 (hetero)aryl and C 7 -C 13 aralkyl,
wherein C 5 -C 7 (hetero)aryl and C 7 -C 13 aralkyl may be substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, and OR 6a .

5. The electrolyte composition (A) according to claim 1 , wherein the compound of formula (I) is selected from the group consisting of compounds of formula (I b) wherein X 1 and X 2 are N(R 1 )

wherein R 8 is selected from the group consisting of H, C 5 -C 7 (hetero)aryl and C 7 -C 13 aralkyl, and R 9 is selected from the group consisting of C 5 -C 7 (hetero)aryl and C 7 -C 13 aralkyl,
wherein C 5 -C 7 (hetero)aryl and C 7 -C 13 aralkyl may be substituted by one or more substituents selected from the group consisting of F, CN, C 1 -C 6 alkyl, and OR 6a .

6. 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 a 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 an acyclic acetal or ketal, which may be partly halogenated,
(f) an orthocarboxylic acid ester, which may be partly halogenated,
(g) a cyclic or a noncyclic ester of a carboxylic acid, which may be partly

Assignees

• Basf Se

Inventors

• Chesneau Frederick Francois
• Baan Zoltan
• Gaspar Boris
• Schmidt Michael
• Garsuch Arnd
• Wolf Hannes
• Leitner Klaus
• Saffert Christian
• Klaus Wolfgang
• Kuhl Melanie

Classifications

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0568

  characterised by the solutes · CPC title