Solid polymer electrolyte composition

Patent metadata

Field	Value
Publication number	US-2016276706-A1
Application number	US-201415030173-A
Country	US
Kind code	A1
Filing date	Oct 20, 2014
Priority date	Oct 18, 2013
Publication date	Sep 22, 2016
Grant date	—

Abstract

A polymer electrolyte composition includes a hard polymer segment covalently bound to an ionically-conducting segment, and a salt that includes an element M selected from an alkali metal, an alkaline earth metal, zinc, and aluminum. The hard polymer segment has a glass transition temperature (T g ) greater than or equal to 110° C., or a melting temperature (T m ) greater than 110° C. The ionically-conducting segment has a molecular weight of 800 to 10,000 g/mol. The polymer electrolyte composition has an ionic conductivity for an M ion greater than or equal to 1×10 −8 S/cm at 25° C. Methods for the preparation of the polymer electrolyte composition are also provided, as are articles (e.g., electrochemical cells and energy storage devices) that contain the polymer electrolyte composition.

First claim

1 . A polymer electrolyte composition comprising:
a hard polymer segment having:
(a) a glass transition temperature (T g ) greater than or equal to 110 ° C.; or
(b) a melting temperature (T m ) greater than 110° C.;
an ionically-conducting segment, said ionically-conducting segment having a molecular weight of 800 to 10,000 g/mol; and a salt comprising an element M, wherein M is selected from an alkali metal, an alkaline earth metal, zinc, and aluminum,
wherein the hard polymer segment is covalently bound to the ionically-conducting segment, and wherein said polymer electrolyte composition has an ionic conductivity for an M ion greater than or equal to 1×10 −8 S/cm at 25° C.

2 . (canceled)

3 . The polymer electrolyte composition according to claim 1 , said polymer electrolyte composition having an ionic conductivity for M ion greater than 1×10 −5 S/cm at 25° C.

4 . The polymer electrolyte composition according to claim 1 , further comprising a plasticizer.

5 . (canceled)

6 . The polymer electrolyte composition according to claim 4 , wherein the plasticizer comprises polyethylene glycol dimethyl ether.

7 . The polymer electrolyte composition according to claim 1 , wherein M is selected from an alkali metal and an alkaline earth metal.

8 . The polymer electrolyte composition according to claim 1 , wherein the hard polymer segment comprises a C 15 to C 80 alkyl group.

9 . The polymer electrolyte composition according to claim 1 , wherein the hard polymer segment comprises polyethylene.

10 . (canceled)

11 . (canceled)

12 . The polymer electrolyte composition according to claim 1 , wherein the ionically-conducting segment comprises 30 to 140 repeating polyethylene oxide units.

13 - 15 . (canceled)

16 . The polymer electrolyte composition according to claim 12 , wherein the hard polymer segment comprises polyethylene and wherein the ionically-conducting segment additionally comprises a benzene ring.

17 . The polymer electrolyte composition according to claim 16 , wherein the ionically-conducting segment comprises a structural unit having the formula:

wherein a represents a number from 40 to 130.

18 . The polymer electrolyte composition according to claim 17 , wherein a represents a number from 70 to 90.

19 . The polymer electrolyte composition according to claim 1 , wherein the ionically-conducting segment comprises a residue from a precursor compound of the formula (I):

wherein a represents a number from 40 to 130.

20 - 24 . (canceled)

25 . The polymer electrolyte composition according to claim 1 , wherein:
M is lithium; said polymer electrolyte composition has an ionic conductivity for Li + greater than or equal to 1×10 −6 S/cm at 25° C.; and said polymer electrolyte composition has a lithium dendrite growth resistance (C d ) value greater than or equal to 1000 C/cm 2 at current density (J) value of 0.26 mA/cm 2 and 90° C.

26 - 37 . (canceled)

38 . The polymer electrolyte composition according to claim 1 , wherein: M is lithium; the hard polymer segment comprises polyethylene; and the ionically-conducting segment comprises a structural unit having the formula:

wherein a represents a number from 40 to 130.

39 . The polymer electrolyte composition according to claim 38 , wherein a represents a number from 70 to 90.

40 . The polymer electrolyte composition according to claim 1 , wherein said polymer electrolyte composition has an ionic conductivity for Li + greater than or equal to 1×10 −6 S/cm at 25° C., and wherein the ionically-conducting segment comprises a residue from a precursor compound of the formula (I):

wherein a represents a number from 40 to 130.

41 . The polymer electrolyte composition according to claim 1 , wherein:
the hard polymer segment comprises polyethylene; the ionically-conducting segment comprises 30 to 140 repeating polyethylene oxide units; and the salt is a lithium salt.

42 - 47 . (canceled)

48 . The polymer electrolyte composition according to claim 41 , wherein the ionically-conducting segment comprises a structural unit having the formula:

wherein a represents a number from 40 to 130.

49 . The polymer electrolyte composition according to claim 48 , wherein a represents a number from 70 to 90.

50 . The polymer electrolyte composition according to claim 41 , wherein the ionically-conducting segment comprises a residue from a precursor compound of the formula (I):

wherein a represents a number from 40 to 130.

51 . The polymer electrolyte composition according to claim 41 , wherein the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium bis(trifluoromethanesulfonimide) (LiN(CF 3 SO 2 ) 2 ), lithium bis(perfluoroethylsulfonylimide) (LiN(C 2 F 5 SO 2 ) 2 ), lithium thiocyanate (LiSCN), lithium dicyanamide (LiN(CN) 2 ), lithium tris(trifluoromethanesulphonyl)methyl (LiC(CF 3 SO 2 ) 3 ), lithium bisoxalatoborate (LiB(C 2 O 4 ) 2 ), lithium oxalatoborates, lithium bis(chelato)borate, lithium alkyl fluorophosphates, LiPF 3 (C 2 F 5 ) 3 , and LiPF 3 (CF 3 ) 3 .

52 . The polymer electrolyte composition according to claim 51 , wherein the lithium salt is LiTFSI.

53 - 62 . (canceled)

63 . An electrochemical cell comprising a separator, said separator comprising the polymer electrolyte composition according to claim 1 .

64 . (canceled)

65 . (canceled)

66 . An energy storage device comprising a plurality of electrochemical cells, wherein at least one of the plurality of electrochemical cells is an electrochemical cell according to claim 63 .

67 . (canceled)

68 . (canceled)

69 . A method for the preparation of the polymer electrolyte composition according to claim 1 , said method comprising:
co-polymerizing a mixture comprising a cycloalkylene compound and a compound comprising the ionically-conducting segment or a precursor thereof in the presence of Grubbs second-generation catalyst, the salt, and solvent; evaporating the solvent to obtain a polymer film; and solid state hydrogenation reaction of the polymer film in the presence of a lithium salt.

70 . The method according to claim 69 , wherein the solvent is tetrahydrofuran (THF).

71 . The method according to claim 70 , wherein the cycloalkylene compound is c

Assignees

• Univ Cornell

Inventors

• Coates Geoffrey W
• Khurana Rachna

Classifications

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title

• C08F290/062

  Polyethers · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M10/0525

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

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title