Acrylonitrile derivatives as additive for electrolytes in lithium ion batteries

Patent metadata

Field	Value
Publication number	US-9761909-B2
Application number	US-201414905630-A
Country	US
Kind code	B2
Filing date	Jul 7, 2014
Priority date	Jul 15, 2013
Publication date	Sep 12, 2017
Grant date	Sep 12, 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 (I) wherein X 1 and X 2 are independently from each other selected from N(R 1 ), P(R 1 ), O, and S, Y 1 and Y 2 are independently from each other selected from (O), (S), (PR 2 ) and (NR 2 ); and electrochemical cells containing electrolyte composition (A).

First claim

The invention claimed is:

1. An electrolyte composition (A) comprising:
(i) an aprotic organic solvent comprising a cyclic organic carbonate or a noncyclic organic carbonate;
(ii) at least one conducting salt;
(iii) at least one compound of formula (I)

wherein
X 1 and X 2 are independently from each other selected from the group consisting of N(R 1 ), P(R 1 ), O, and S;
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 13 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 ;
Y 1 and Y 2 are independently from each other selected from the group consisting of (O),(S), (PR 2 ) and (NR 2 ),
R 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, (hetero)C 3 -C 6 cycloalkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, C 7 -C 13 aralkyl, OR 2a and C(O)R 2a , 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 2b , OS(O) 2 R 2b , S(O) 2 R 2b , OR 2b , C(O)R 2b , C(O)OR 2b , NR 2b R 2c , and NC(O)R 2b R 2c ; and
R 2a , R 2b and R 2c 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, 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,
R 3 , R 4 , R 3a , and R 3b 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, 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 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, at least one further additive.

2. The electrolyte composition (A) according to claim 1 wherein both Y 1 and Y 2 are the same and each selected from the group consisting of (O) and NR 1 .

3. The electrolyte composition (A) according to claim 1 , wherein the at least one compound of formula (I) is compound (I.1)

4. The electrolyte composition (A) according to claim 1 , wherein the at least one compound of formula (I) is selected from a compound of formula (I), wherein X 1 and X 2 are independently from each other selected from N(R 1 ) and O.

5. The electrolyte composition (A) according to claim 1 , wherein the aprotic organic solvent (i) is selected from the group consisting of
(a) cyclic and noncyclic organic carbonates, which may be partly halogenated,
(b) di-C 1 -C 10 -alkylethers, which may be partly halogenated,
(c) di-C 1 -C 4 -alkyl-C 2 -C 6 -alkylene ethers and polyethers, which may be partly halogenated,
(d) cyclic ethers, which may be partly halogenated,
(e) cyclic and acyclic acetals and ketals, which may be partly halogenated,
(f) orthocarboxylic acids esters, which may be partly halogenated,
(g) cyclic and noncyclic esters of carboxylic acids, which may be partly halogenated,
(h) cyclic and noncyclic sulfones, which may be partly halogenated,
(i) cyclic and noncyclic nitriles and dinitriles, which may be partly halogenated, and
(j) ionic liquids, which may be partly halogenated.

6. The electrolyte composition (A) according to claim 1 , wherein the electrolyte composition (A) contains at least one aprotic solvent (i) selected from cyclic organic carbonates and at least one aprotic organic solvent (i) selected from noncyclic organic carbonates.

7. 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 I ) 4 ], Li[B(R I ) 2 (OR II O )] and Li[B(OR II O ) 2 ] wherein each R I is independently from each other 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 III , wherein R III 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 II 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 the both oxygen atoms with the central B-atom;
LiClO 4 ; LiAsF 6 ; LiCF 3 SO 3 ; Li 2 SiF 6 ; LiSbF 6 ; LiAlCl 4 , lithium tetrafluoro (oxalato) phosphate; lithium oxalate; and salts of the general formula Li[Z(C n F 2n+1 SO 2 ) m ,], where m and n are defined as follows:
m=1 when Z is selected from the group consisting of oxygen and sulfur,
m=2 when Z is selected from the group consisting of nitrogen and phosphorus,
m=3 when Z is selected from the group consisting of carbon and silicon, and n is an integer in the range from 1 to 20.

8. The electrolyte composition (A) according to claim 1 , wherein the electrolyte composition (A) contains at least one further additive (iv) which is selected from the group consisting of vinylene carbonate and its derivatives, vinyl ethylene carbonate and its derivatives, methyl ethylene carbonate and its derivatives, lithium (bisoxalato) borate, lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato) phosphate, lithium oxalate, 2-vinyl pyridine, 4-vinyl pyridine, cyclic exo-methylene carbonates, sultones, organic esters of inorganic acids, acyclic and cyclic alkanes having a boiling point at 1 bar of at least 36° C., and aromatic compounds, optionally halogenated cyclic and acyclic sulfonylimides, optionally halogenated cyclic and acyclic phosphate esters, optionally halogenated cyclic and acyclic phosphines, optionally halogenated cyclic and acyclic phosphites, optionally halogenated cyclic and acyclic phosphazenes, optionally halogenated cyclic and acyclic silylamines, optionally halogenated cyclic and acyclic halogenated esters, optionally halogenated cyclic and acyclic amides, optionally halogenated cyclic and acyclic anhydrides, ionic liquids, and optionally halogenated org

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

• H01M4/0404

  by coating on electrode collectors · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M2220/30

  Batteries in portable systems, e.g. mobile phone, laptop · CPC title

• H01M2004/027

  Negative electrodes · CPC title