Polymeric materials for electrochemical cells and ion separation processes

Patent metadata

Field	Value
Publication number	US-2020306745-A1
Application number	US-202016898052-A
Country	US
Kind code	A1
Filing date	Jun 10, 2020
Priority date	Apr 3, 2015
Publication date	Oct 1, 2020
Grant date	—

Abstract

Polymers of intrinsic microporosity are provided herein. Disclosed polymers of intrinsic microporosity include modified polymers of intrinsic microporosity that include negatively charged sites or crosslinking between monomer units. Systems making use of polymers of intrinsic microporosity and modified polymers of intrinsic microporosity are also described, such as electrochemical cells and ion separation systems. Methods for making and using polymers of intrinsic microporosity and modified polymers of intrinsic microporosity are also disclosed.

First claim

What is claimed is:

1 . A modified polymer of intrinsic microporosity comprising a polymer of intrinsic microporosity having a plurality of repeat units, wherein at least one of the repeat units includes one or more negative charges, or wherein the polymer of intrinsic microporosity is crosslinked, or both.

2 . The modified polymer of intrinsic microporosity of claim 1 , wherein at least one of the repeat units includes a negatively charged nitrogen site, a negatively charged oxygen site, a negatively charged sulfur site, a negatively charged carbon site, or any combination thereof.

3 . The modified polymer of intrinsic microporosity of claim 1 , wherein at least one of the repeat units includes one or more charged moieties selected from the group consisting of:

where subscript m and subscript o are independently integers selected from 1 to 8.

4 . The modified polymer of intrinsic microporosity of claim 1 , wherein at least one the repeat units have a structure selected from the group consisting of:

where subscript m and subscript o are independently integers selected from 1 to 8, and wherein subscript n is an integer selected from 10 to 1000.

5 . The modified polymer of intrinsic microporosity of claim 1 , wherein at least one repeat unit is crosslinked with a non-adjacent repeat unit.

6 . The modified polymer of intrinsic microporosity of claim 1 , wherein at least one repeat unit is crosslinked with a non-adjacent repeat unit by a crosslinker selected from the group consisting of 2,6-bis(4-azidobenzylidene)cyclohexanone, 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, 2,6-bis(4-azidobenzylidene)-4-ethylcyclohexanone, 4-azidophenylsulfone, and any combination of these.

7 . The modified polymer of intrinsic microporosity of claim 1 , wherein a surface area of the polymer of intrinsic microporosity is at least 300 m 2 /g.

8 . The modified polymer of intrinsic microporosity of claim 1 , further comprising a support membrane in contact with the polymer of intrinsic microporosity.

9 . A method of making a modified polymer of intrinsic microporosity comprising:
forming a reaction mixture comprising a polymer of intrinsic microporosity and a reducing agent, or a nucleophile, or a crosslinking agent, or any combination thereof under conditions sufficient to form the modified polymer of intrinsic microporosity; wherein the modified polymer of intrinsic microporosity comprises a plurality of repeat units; and wherein at least one of the repeat units includes one or more negative charges, or wherein the modified polymer of intrinsic microporosity is crosslinked, or both.

10 . The method of claim 9 , wherein reaction between the polymer of intrinsic microporosity and the reducing agent or the nucleophile generates the one or more negative charges.

11 . The method of claim 10 , wherein the reducing agent comprises one or more of an alkali metal polysulfide, Li 2 S m where subscript m is an integer selected from 2 to 100, an alkali metal sulfide, ammonium sulfide, an alkali metal hydrogen sulfide, an alkali metal, a metallocene, an alkali metal naphthalenide, an inorganic reducing agent having an oxidation potential at or below 0.0 V vs. a standard hydrogen electrode (SHE), and an organic reducing agent having an oxidation potential at or below 0.0 V vs. SHE.

12 . The method of claim 10 , wherein the nucleophile comprises one or more of an alkali metal polysulfide, Li 2 S m where subscript m is an integer selected from 2 to 100, an alkali metal sulfide, ammonium sulfide, an alkali metal hydrogen sulfide, an alkali metal alkylsulfide, an alkali metal arylsulfide, P 2 S 5 , and an alkali metal sulfite.

13 . The method of claim 9 , wherein reaction between the polymer of intrinsic microporosity and the crosslinking agent induces crosslinking of the polymer of intrinsic microporosity by generating one or more covalent bonds between a first repeat unit and a second repeat unit that is not adjacent to the first repeat unit.

14 . The method of claim 13 , wherein the crosslinking agent comprises one or more of 2,6-bis(4-azidobenzylidene)cyclohexanone, 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, 2,6-bis(4-azidobenzylidene)-4-ethylcyclohexanone, 4-azidophenylsulfone, oxygen, and any combination of these.

15 . The method of claim 9 , wherein forming a reaction mixture comprising a polymer of intrinsic microporosity and a crosslinking agent comprises inducing a crosslinking reaction of the polymer of intrinsic microporosity by exposure of the polymer of intrinsic microporosity to one or more of ultraviolet radiation, microwave radiation, and heat.

16 . The method of claim 9 , wherein the reaction mixture comprises a reducing agent, or a nucleophile, or both, and wherein at least one of the repeat units includes one or more negative charges.

17 . An electrochemical cell comprising:
an anode; an anode electrolyte in contact with the anode; a separator in contact with the anode electrolyte, wherein the separator comprises a polymer of intrinsic microporosity; a cathode electrolyte in contact with the separator; and a cathode in contact with the cathode electrolyte.

18 . The electrochemical cell of claim 17 , wherein the separator further comprises a support membrane in contact with the polymer of intrinsic microporosity.

19 . The electrochemical cell of claim 18 , wherein the support membrane comprises a polymer selected from the group consisting of: polyethylene, polyethylene copolymers, polypropylene, polypropylene copolymers, polyacrylonitrile, polyacrylonitrile copolymers, poly(vinylidene fluoride), poly(tetrafluoroethylene), poly(vinyl chloride), poly(vinylchloride) copolymers, poly(hexafluoropropylene), poly(hexafluoropropylene) copolymers, polyaramide, any combination thereof, and any copolymers thereof

20 . The electrochemical cell of claim 18 , wherein the support membrane has a melting temperature, and wherein exposing the support membrane to a temperature exceeding the melting temperature causes at least a portion of the support membrane to melt and close pores within the separator.

Assignees

• Univ California

Inventors

• Helms Brett A
• Li Changyi
• Ward Ashleigh
• Doris Sean E
• Frischmann Peter D

Classifications

• B01D2325/0283

  Pore size · CPC title

• B01D69/02 Primary

  characterised by their properties · CPC title

• C08J5/2256

  based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation · CPC title

• C07D493/22

  in which the condensed system contains four or more hetero rings · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title