Polymers for use as protective layers and other components in electrochemical cells

Patent metadata

Field	Value
Publication number	US-10243202-B2
Application number	US-201314068333-A
Country	US
Kind code	B2
Filing date	Oct 31, 2013
Priority date	Nov 2, 2012
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

Electrode structures and electrochemical cells are provided. The electrode structures and/or electrochemical cells described herein may include one or more protective layers comprising a polymer layer and/or a gel polymer electrolyte layer. The polymer layer may be formed from the copolymerization of an olefinic monomer comprising at least one electron withdrawing group and an olefinic comonomer comprising at least one electron donating group. Methods for forming polymer layers are also provided.

First claim

What is claimed is:

1. An electrochemical cell comprising:
an electroactive layer; and
at least one layer comprising a polymer, wherein the polymer is formed from:
a) the copolymerization of at least one olefinic monomer comprising a maleimide, at least one electron withdrawing group, and at least one olefinic comonomer, different than the olefinic monomer, and comprising at least one electron donating group, or
b) the polymerization of an olefinic monomer comprising a maleimide having at least two double bonds, at least one electron withdrawing group, and at least one electron donating group, with at least one olefinic comonomer, different than the olefinic monomer,
wherein the polymer includes structural units comprising the at least one electron withdrawing group that alternate with structural units comprising the at least one electron donating group;
wherein the electron withdrawing group is selected from the group consisting of a haloalkyl, —CN, —CON(R 1 ) 2 , —CONR 1 H, halogen, —NO 2 , SO 3 R 1 , —SO(OR 1 ) 2 , —SO(OR 1 )H, —SOR 1 , —SO 2 R 1 , —PO(OR 1 ) 2 , —PO(OR 1 )H, and protonated amine groups;
wherein R 1 may be linked to at least one further electron donating or electron withdrawing group;
wherein each occurrence of R 1 is independently selected from the group consisting of hydrogen; halogen; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; a metal ion, and a lithium-containing group;
wherein a gel state ion conductivity of the polymer is greater than or equal to 10 −4 S/cm; and
wherein the electron withdrawing group and/or the electron donating group comprises a heteroaryl group.

2. An electrochemical cell as in claim 1 , wherein:
a) in the copolymerization of the at least one olefinic monomer comprising at least one electron withdrawing group and at least one olefinic comonomer comprising at least one electron donating group, the at least one electron withdrawing group is attached to a double bond and the at least one electron donating group is attached to a double bond, or
b) in the polymerization of the olefinic monomer having at least two double bonds, the at least one electron withdrawing group is attached to a double bond and the at least one electron donating group is attached to another of the double bonds.

3. An electrochemical cell as in claim 1 ,
wherein the electron donating group is selected from the group consisting of an alkylamino, a heteroaryl, a cycloalkyl, a cycloalkenyl, a cycloalkynyl, —OCOR 2 , —NR 2 COR 2 , —OR 2 , —SR 2 , —Si(OR 2 ) 3 , —Si(OR 2 ) 2 H, —Si(OR 2 )H 2 , —Si(R 2 ) 3 , —Si(R 2 ) 2 H, —Si(R 2 )H 2 ,

wherein each occurrence of R 2 is independently selected from the group consisting of hydrogen; substituted or unsubstituted, branched or unbranched aliphatic; substituted or unsubstituted cyclic; substituted or unsubstituted, branched or unbranched acyclic; substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl, substituted or unsubstituted, branched or unbranched alkylene oxide or poly(alkylene oxide); a metal ion; an anionic group, and a lithium-containing conducting group;
wherein n is 1, 2 or 3; and
wherein R 2 may optionally be linked to at least one further electron donating or electron withdrawing group attached to an olefinic double bond.

4. An electrochemical cell as in claim 1 , wherein at least one of the olefinic monomers comprises at least two double bonds, wherein each double bond has attached thereto one or more electron donating groups or one or more electron withdrawing groups.

5. An electrochemical cell as in claim 1 , wherein the polymer is formed by copolymerization of at least one maleimide and at least one vinyl ether, or by polymerization of an olefinic monomer including at least one maleimide and at least one vinyl ether.

6. An electrochemical cell as in claim 1 , wherein the olefinic monomer comprising the at least one electron withdrawing group is selected from the group consisting of

wherein R 1 is independently selected from the group consisting of hydrogen; halogen; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl, a metal ion, and a lithium-containing group; and
wherein R 1 may be linked to at least one further electron donating or electron withdrawing group attached to an olefinic double bond.

7. An electrochemical cell according to claim 1 , wherein:
the olefinic monomer comprising the at least one electron withdrawing group is selected from a monomer according to formula (I)

wherein
R 3 is —(CH 2 ) m —O—(CHR 4 —CH 2 —O) n —R 5 ;
R 4 is methyl or hydrogen;
R 5 is C 1 -C 4 -alkyl;
m is 0 or 1;
n is an integer from 1 to 50; and
R 3 is located at the benzene cycle in ortho-, meta- or para-position (in relation to the maleimide cycle).

8. An electrochemical cell as in claim 1 , wherein the electron withdrawing group and/or the electron donating group comprises a cycloalkyl group, a cycloalkenyl group, or a cycloalkynyl group.

9. An electrochemical cell as in claim 1 , wherein the heteroaryl group comprises a nitrogen heteroatom, two nitrogen heteroatoms, or an oxygen heteroatom.

10. An electrochemical cell as in claim 1 , wherein the polymer comprises a substituted or unsubstituted, branched or unbranched poly(alkylene oxide); an anionic group; and/or a lithium-containing group.

11. An electrochemical cell as in claim 10 , wherein the lithium-containing group is Aryl-SO 3 Li or Alkyl-SO 3 Li.

12. An electrochemical cell as in claim 3 , wherein R 1 and/or R 2 comprises a lithium ion and/or is conductive to lithium ions.

13. An electrochemical cell as in claim 1 , wherein the electroactive layer comprises lithium metal.

14. An electrochemical cell as in claim 1 , wherein the layer comprising the polymer is a gel polymer electrolyte layer.

15. An electrochemical cell as in claim 1 , wherein the polymer comprises a lithium salt.

16. An electrochemical cell as in claim 15 , wherein the lithium salt is intrinsic to the polymer.

17. An electrochemical cell as in claim 1 , wherein at least one of the monomer and comonomer, or the olefinic monomer having at least two double bonds, comprises at least one functional group selected from the group consisting of poly(ethylene oxide), lithiated sulfonate groups, lithiated carboxylate groups, and lithiated trifluoromethanesulfonylimide groups.

18. An electrochemical cell comprising:
an electroactive layer; and
at least one layer comprising a polymer, wherein the polymer includes structural units comprising a maleimide comprising an electron withdrawing group that alternate with structural units comprising an electron donating group, wherein the structural units comprising the maleimide are different than the structural units comprising the electron donating group;
wherein the electron withdrawing group is selected from the group consisting of a haloalkyl, —CN, —CON(R 1 ) 2 , —CONR 1 H, halo

Assignees

• Sion Power Corp
• Basf Se

Inventors

• Fleischmann Sven
• Petsch Tobias
• Misske Andrea
• Schmidt Ruediger
• Viner Veronika G
• Sankaran Bala

Classifications

• H01M10/0565

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

• H01M4/366

  as layered products · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M4/139 Primary

  Processes of manufacture · CPC title

• H01M4/622

  being polymers · CPC title