Use of reactive lithium alkoxyborates as electrolyte additives in electrolytes for lithium ion batteries

Patent metadata

Field	Value
Publication number	US-2016164142-A1
Application number	US-201414906198-A
Country	US
Kind code	A1
Filing date	Jul 11, 2014
Priority date	Jul 19, 2013
Publication date	Jun 9, 2016
Grant date	—

Abstract

An electrolyte composition (A) containing (i) at least one aprotic organic solvent, (ii) at least one conducting salt different from the at least one compound of formula (I), (iii) at least one compound of formula (I), wherein R 1 , R 2 , R 3 , and R 4 are selected from C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 10 cycloalkyl, C 6 -C 14 aryl and C 5 -C 14 heteroaryl and wherein R 4 is different from each R 1 , R 2 , and R 3 , (iv) optionally at least one further additive.

First claim

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

wherein
R 1 , R 2 , R 3 , and R 4 are each independently selected from C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 10 cycloalkyl, C 6 -C 14 aryl and C 5 -C 14 heteroaryl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl may be substituted by one or more substituents selected from F, CN, OR 5 ,

and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, and benzyl,
wherein R 4 is different from each R 1 , R 2 , and R 3 ,
R 5 is selected from H, oligo C 1 -C 4 alkylene oxide with 2 to 10 alkylene oxide units, and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, benzyl, and C(O)OC 1 -C 10 alkyl,
R 6 is selected from H, F and optionally fluorinated C 1 -C 4 alkyl; and
(iv) optionally, a further additive.

2 . The electrolyte composition according to claim 1 , wherein the compound of formula (I) is selected from compounds of formula (I) wherein
R 1 , R 2 , R 3 , and R 4 are selected independently from each other from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 6 -C 14 aryl and C 5 -C 14 heteroaryl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl may be substituted by one or more substituents selected from F, CN, OR 5 ,

and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, and benzyl,
R 5 is selected from H, oligo C 2 -C 3 alkylene oxide with 2 to 10 alkylene oxide units, and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, benzyl, and C(O)OC 1 -C 4 alkyl,
R 6 is selected from H, F and optionally fluorinated C 1 -C 4 alkyl.

3 . The electrolyte composition according to claim 1 , wherein the compound of formula (I) is selected from compounds of formula (I) wherein
R 1 , R 2 , and R 3 are optionally fluorinated C 1 -C 6 alkyl, and R 4 is selected from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 6 -C 14 aryl and C 5 -C 14 heteroaryl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl may be substituted by one or more groups selected from F, CN, OR 5 ,

and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, and benzyl,
R 5 is selected from H, oligo C 1 -C 4 alkylene oxide with 2 to 10 alkylene oxide units, and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, benzyl, and C(O)OC 1 -C 4 alkyl,
R 6 is selected from H, F and optionally fluorinated C 1 -C 4 alkyl.

4 . The electrolyte composition according to claim 1 , wherein the compound of formula (I) is selected from compounds of formula (I) wherein
R 1 , R 2 , and R 3 are CH 3 , and R 4 is selected from C 2 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 10 cycloalkyl, C 6 -C 14 aryl and C 5 -C 14 heteroaryl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl may be substituted by one or more substituents selected from F, CN, OR 5 ,

and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, and benzyl,
R 5 is selected from H, oligo C 1 -C 4 alkylene oxide with 2 to 10 alkylene oxide units, and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, benzyl, and C(O)OC 1 -C 10 alkyl, and
R 6 is selected from H, F and optionally fluorinated C 1 -C 4 alkyl.

5 . The electrolyte composition according to claim 1 , wherein the compound of formula (I) is selected from compounds of formula (I) wherein
R 1 , R 2 , and R 3 are CH 3 , and R 4 is selected from C 2 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 6 aryl and C 5 -C 7 heteroaryl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl may be substituted by one or more groups selected from F, CN, OR 5 ,

and optionally fluorinated groups selected from C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, and benzyl, and
R 5 is selected from H, oligo C 2 -C 3 alkylene oxide with 2 to 10 alkylene oxide units, and optionally fluorinated groups selected from C 1 -C 4 alkyl, phenyl, benzyl, and C(O)OC 1 -C 4 alkyl,
R 6 is selected from H, F and optionally fluorinated C 1 -C 4 alkyl.

6 . The electrolyte composition according to claim 1 , wherein the compound of formula (I) is at least one selected from the group consisting of lithium 3-allyl trimethyl borate, lithium 3-propargyl trimethyl borate, lithium phenyl trimethyl borate, lithium 4-pyridyl trimethyl borate, lithium 3-pyridyl trimethyl borate, lithium 2-pyridyl trimethyl borate, lithium 2,2,2-trifluoroethyl trimethyl borate, lithium glycerol carbonate trimethyl borate, lithium ethylene glycol methyl ether trimethyl borate, lithium diethylene glycol methyl ether trimethyl borate, lithium 4-fluorophenyl trimethyl borate, lithium 2-butynyl trimethyl borate, 3-propionitrile trimethyl borate, and lithium trifluoroethyl trimethyl borate.

7 . The electrolyte composition according to claim 1 , wherein the aprotic organic solvent (i) is selected from
(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, and (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.

8 . The electrolyte composition according to claim 1 , wherein the electrolyte composition comprises a conducting salt (ii) different from the compound of formula (I), the conducting salt (ii) being 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 10 ) 4 ], Li[B(R 10 ) 2 (OR 11 O)] and Li[B(OR 11 O) 2 ],
wherein each R 10 is independently from each other selected from 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 12 , wherein R 12 is selected from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 2 -C 6 alkynyl, and
wherein (OR 11 O) is a bivalent group derived from a 1,2- or 1,3-diol, from a 1,2- or 1,3-dicarboxlic acid or from a 1,2- or 1,3-hydroxycarboxylic acid, wherein the

Assignees

• Basf Se
• Rhode Island Board Of Education State Of Rhode Island And Providence Plantations

Inventors

• Garsuch Arnd
• Schmidt Michael
• Lucht Brett
• Xu Mengqing
• Zhou Liu

Classifications

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/505

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

• H01M10/0568

  characterised by the solutes · CPC title

• H01M4/387

  Tin or alloys based on tin · CPC title

• H01M10/0525

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