Acrylonitrile derivatives as additive for electrolytes in lithium ion batteries

Patent metadata

Field	Value
Publication number	US-2017288288-A1
Application number	US-201715623205-A
Country	US
Kind code	A1
Filing date	Jun 14, 2017
Priority date	Jul 15, 2013
Publication date	Oct 5, 2017
Grant date	—

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

1 : An electrolyte composition (A), comprising:
at least one aprotic organic solvent; at least one conducting salt; at least one compound of formula (I)

wherein
X 1 and X 2 are each independently N(R 1 ), P(R 1 ), O, or S;
R 1 is 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 , or 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 each independently (O), (S), (PR 2 ) and or (NR 2 ),
R 2 is 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 or 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 each independently H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 10 alkenyl, or C 5 -C 7 (hetero)aryl, wherein alkyl, (hetero)cycloakyl, alkenyl, and (hetero)aryl may be substituted by one or more substituents selected from F and CN,
R 3 , R 4 , R 3a , and R 3b are each independently 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, or 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 each independently H, C 1 -C 10 alkyl, C 3 -C 6 (hetero)cycloalkyl, C 2 -C 6 alkenyl, or C 5 -C 7 (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and (hetero)aryl may be substituted by one or more substituents selected from 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 are (O) or 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 a compound of formula (I) wherein X 1 and X 2 are each independently N(R 1 ) or 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 optionally partly halogenated, (b) di-C 1 -C 10 -alkylethers, optionally partly halogenated, (c) di-C 1 -C 4 -alkyl-C 2 -C 6 -alkylene ethers and polyethers, optionally partly halogenated, (d) cyclic ethers, optionally partly halogenated. (e) cyclic and acyclic acetals and ketals, optionally partly halogenated, (f) orthocarboxylic acids esters, optionally partly halogenated, (g) cyclic and noncyclic esters of carboxylic acids, optionally partly halogenated, (h) cyclic and noncyclic sulfones, optionally partly halogenated, (i) cyclic and noncyclic nitriles and dinitriles, optionally partly halogenated, and (j) ionic liquids, optionally partly halogenated.

6 . The electrolyte composition (A) according to claim 1 , wherein the electrolyte composition (A) comprises 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 F, Cl, Br, I, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, or 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 formula Li[Z(C n F 2n+1 SO 2 ) m ], wherein m=1 when Z is selected from oxygen and sulfur, m=2 when Z is selected from nitrogen and phosphorus, m=3 when Z is selected from 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) further comprises at least one additive (iv) 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 organic heterocycles.

9 . The electrolyte composition (A) according to claim 1 , wherein the concentration of the at least one compound of formula (I) is 0.001 to 10 wt-%, based on the total weight of the electrolyte composition (A).

10 . The electrolyte composition (A) according claim 1 , wherein the concentration of the at least one compound of formula (I) is from 0.01 to 2 wt.-%, based on the total weight of the electrolyte composition (A).

11 . A method to prepare an electrolyte for an electrochemical cell, comprising:
adding a compound of formula (I) to the electrolyte:

wh

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

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M2220/10

  Batteries in stationary systems, e.g. emergency power source in plant · CPC title

• H01M4/0404

  by coating on electrode collectors · CPC title