Design of ligand attachment chemistry for high conductivity polymer electrolytes

Patent metadata

Field	Value
Publication number	US-2021284805-A1
Application number	US-202117191422-A
Country	US
Kind code	A1
Filing date	Mar 3, 2021
Priority date	Mar 3, 2020
Publication date	Sep 16, 2021
Grant date	—

Abstract

A composition of matter useful in an electrolyte, comprising a polymer including: a repeat unit, the repeat unit including a backbone section; and a side chain attached to the backbone section, wherein the side chain includes a ligand moiety configured to ionically bond to a lithium ion. The polymer has a glass transition temperature (e.g., less than room temperature) wherein the polymer is in a solid state during operation of a lithium ion battery comprising an electrolyte including the polymer.

First claim

What is claimed is:

1 . A polymer, comprising:
a plurality of repeat units, each of the repeat units including a backbone section; and a plurality of side chains, each of the side-chains attached to a different one of the backbone sections, wherein: at least, some of the side chains include a spacer connected to a ligand moiety, the ligand moiety configured to bond to, or interact with, a cation so as to at least solvate or conduct the cation, the spacer does not conduct or solvate the cation, and the spacer is 4 atoms-20 atoms long.

2 . The polymer of claim 1 , wherein the glass transition temperature is less than 40 degrees Celsius or less than 50 degrees Celsius.

3 . The polymer of claim 1 , wherein the spacer at least:
does not include nitrogen or oxygen, or consists essentially of at least one of carbon, silicon, sulfur, phosphorus, hydrogen.

4 . The polymer of claim 1 , wherein the spacer comprises at least one of an alkane, an ether, a siloxane, a thiol ether.

5 . The polymer of claim 1 , wherein the ligand moiety comprises an electron rich group or a group comprising an electron lone pair.

6 . The polymer of claim 1 , wherein the spacer does not include an amide.

7 . The polymer of claim 1 , wherein the ligand moiety comprises an imidazole or cyano.

8 . The polymer of claim 1 , wherein the polymer has one of the following structures:

wherein BR, BR1, BR2 comprise the backbone section, L1 and SC comprise the spacer, LU, LU1, LU2 comprise the ligand moiety, and x, y, and N are integers and wherein the ligand moiety comprises at least one group selected from:

9 . The polymer of claim 8 , wherein the backbone section comprises one of the following:

and n and m are integers in a range of 5-5000.

10 . The polymer of claim 1 , wherein:
the polymer has a ligand moiety content such that the Li + to ligand moiety molar ratio in an electrolyte comprising the polymer is in a range of 0.07 and 0.6, and/or the polymer has a ligand moiety such that the glass transition temperature is below 40 degrees Celsius and the polymer has the conductivity for the cation, comprising a lithium ion, of at least 10 −5 cm −1 at the temperature of 30 degrees Celsius.

11 . The polymer of claim 1 , wherein the grafting density of the sidechains is in a range of 50% to 90% and is tailored for a conductivity of a Lithium ion in an electrolyte comprising the polymer.

12 . The polymer of claim 1 , wherein not ail the sidechains comprise the ligand moiety.

13 . The polymer of claim 1 , wherein the polymer comprises a bottlebrush polymer.

14 . An electrolyte comprising the polymer of claim 1 , wherein the cation is Li + .

15 . The electrolyte of claim 14 , further comprising an additive for increasing the conductivity of the cation in the electrolyte.

16 . A battery comprising the electrolyte of claim 14 in contact with an anode and a cathode, wherein the polymer has the ligand moiety configured for solvating and conducting the lithium ions in the electrolyte and having a glass transition temperature such that the polymer is in a solid state during operation of the lithium ion batten with the electrolyte comprising the polymer.

17 . A polymer comprising the structure:

where m and n are integers, M is a monomer unit, and S is Sulfur or Carbon.

18 . The polymer of claim 17 , wherein m is in the range 5-15 or 4-20.

19 . A method of making an electrolyte in a lithium ion battery comprising:
providing a polymer having a ligand moiety configured for solvating and conducting lithium ions in the electrolyte and having a glass transition temperature such that the polymer is in a solid state during operation of the lithium ion battery with the electrolyte comprising the polymer; and controlling a grafting density or content of the ligand moiety so that the conductivity is at least 10 −5 S cm −1 at 30 degrees Celsius and the glass transition temperature is below 40 degrees Celsius.

20 . The method of claim 19 , wherein providing the polymer comprises:
(a) combining at least one of an imidazole, pyrazole, triazole, pyridine, oxazole, thiazole, furan, nitrile, or pyrimidine, with an alkane to form a derivative; (b) combining sulfur with the derivative to form a thiol; and (c) combining the thiol with a polymer comprising a siloxane to form the polymer comprising a side chain including the thiol, wherein the combining (c) comprises a thiolene click reaction.

Assignees

• Univ California

Inventors

• Segalman Rachel A
• Hawker Craig J
• Clement Raphaele
• De Alaniz Javier Read
• Michenfelder-Schauser Nicole
• Richardson Peter
• Nikolaev Andrei
• Sample Caitlin
• Wang Hengbin

Classifications

• H01M2300/0082

  Organic polymers · CPC title

• H01M10/0565

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

• Y02E60/10

  Energy storage using batteries · CPC title

• C08G77/26 Primary

  nitrogen-containing groups · CPC title

• C08G77/32 Primary

  Post-polymerisation treatment · CPC title