Doped polymer electrolytes and methods of making and using the same

1. A polymer electrolyte, comprising:

a cationic-functionalized polymer comprising a polymer and least one cationic functional group, wherein the polymer is selected from a polyaryl polymer, a polyarylamide, a polyimide, a polystyrene, a polysulfone, a polyether, a polyether sulfone, a polyketone, a polyetherketone, a polyarylether, a polyolefin, or a polynitrile, and wherein the at least one cationic functional group (CFG) is selected from ammonium [—NH 3 + ,

imidazolium

guanidinium

phosphazenium

sulfonium [sulfonium

oxonium

piperidinium

pyridinium

quinolinium

and phosphonium

wherein R 1 , R 2 , and R 3 are independently hydrogen, aliphatic, aryl, or heteroaryl; and

a polyacid dopant having a structure satisfying a formula R—[PO(OH) 2 ] n or R—[S(O) 2 OH] n wherein R comprises an aliphatic or aromatic group and n is an integer selected from 2 to 4.

2. The polymer electrolyte of claim 1 , wherein the cationic-functionalized polymer has a structure satisfying Formula I

[Polymer repeating unit] m -[Optional Linker] s -[Cationic Functional Group (CFG)] n    Formula I

where m is an integer ranging from two or more; s is an integer ranging from 0 up to m; and n of Formula I is an integer ranging from 1 to at least s.

3. The polymer electrolyte of claim 1 , wherein the cationic-functionalized polymer has a structure satisfying Formula II or Formula III

wherein each of R 1 , R 2 , R 3 , R 4 , and R 6 as recited in Formulas II and III independently is selected from hydrogen, fluoro, an aliphatic group, an aryl group, or a combination thereof; each R 5 independently is selected from an aliphatic group, an aryl group, or a combination thereof; each R 7 independently is selected from aliphatic, aryl, carbonyl, sulfonyl, or a combination thereof; each X independently is selected from ammonium, sulfonium, phosphonium, guanidinium, oxonium, imidazolium, quinolinium, piperidinium, pyridinium, phosphazinium, or combinations thereof; n of Formula II and/or Formula III ranges from 2 to 1000; m ranges from 1 to 4; and p ranges from 0 to 3.

4. The polymer electrolyte of claim 3 , wherein the cationic-functionalized polymer is a polyphenylene having structure satisfying Formula IV or Formula IVC

where m is 2 to 1000, n of Formula IV and/or Formula IVC is at least 1 up to the number of total positions available on each monomeric unit, CFG is the cationic functional group, which is coupled to the polyphenylene, and p is 1 to n as defined for Formula II and/or Formula III.

5. The polymer electrolyte of claim 3 , wherein the cationic-functionalized polymer has a structure satisfying one or more of Formulas IVE-IVM

where q is from 1 to 10; p is 1 to n as defined for Formula II and/or Formula III; CFG is the cationic functional group; and R 1 , R 2 , and R 3 are independently hydrogen, C 1-10 alkyl, or benzyl.

6. The polymer electrolyte of claim 1 , wherein the cationic-functionalized polymer has a structure satisfying any one or more of Formulas VA, VC, or VE

wherein:

m is from two up to the number of monomeric subunits coupled to form a particular polymeric species;

p is from 1 to the number of possible positions available on the monomeric unit;

R 5 is a substituent selected from alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylthio, acyl, aldehyde, amide, amino, aminoalkyl, aryl, arylalkyl, carboxyl, cyano, cycloalkyl, dialkylamino, halo, haloaliphatic, heteroaliphatic, heteroaryl, heterocycloaliphatic, hydroxyl, nitrile, oxo, sulfonamide, sulfhydryl, or thioalkoxy;

n of Formulas VA, VC, and/or VE is from 1 to at least m;

r is 0 to 4; and

x is from 0 to 0.99.

7. The polymer electrolyte according to claim 1 , wherein the cationic-functionalized polymer is a polyether sulfone having a structure satisfying Formula VIIA

wherein:

R 5 is a substituent selected from alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylthio, acyl, aldehyde, amide, amino, aminoalkyl, aryl, arylalkyl, carboxyl, cyano, cycloalkyl, dialkylamino, halo, haloaliphatic, heteroaliphatic, heteroaryl, heterocycloaliphatic, hydroxyl, nitrile, oxo, sulfonamide, sulfhydryl, or, thioalkoxy;

m is two or more up to the number of monomeric subunits coupled to form a particular polymeric species;

n of Formula VIIA is from 1 to at least m;

p is from 1 to 5;

r is from 0 to 4; and

X is not present, or X is selected from SO, SO 2 , CO, O, S

or combinations thereof.

8. The polymer electrolyte according to claim 1 , wherein the cationic-functionalized polymer is a polyketone having a structure satisfying Formula VIIIB

or a polyetherketone having a structure satisfying Formula VIIID

wherein:

L is a linker;

R 5 is a substituent selected from alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylthio, acyl, aldehyde, amide, amino, aminoalkyl, aryl, arylalkyl, carboxyl, cyano, cycloalkyl, dialkylamino, halo, haloaliphatic, heteroaliphatic, heteroaryl, heterocycloaliphatic, hydroxyl, nitrile, oxo, sulfonamide, sulfhydryl, or thioalkoxy;

m is two or more up to the number of monomeric subunits coupled to form a particular polymeric species;

n of Formulas VIIIB and/or VIIID is from 1 to at least m;

p is 1 to 5; and

r is from 0 to 4.

9. The polymer electrolyte of claim 1 , wherein the cationic-functionalized polymer comprises a halogenated polyarylether or a nitrile-containing polyaryl ether having a structure satisfying Formula XB

wherein:

L is a linker;

R 5 is a halogen or nitrile;

m is two or more up to the number of monomeric subunits coupled to form a particular polymeric species;

n of Formula XB is from 1 to at least m;

p is from 1 to 5; and

r is from 0 to 4.

10. The polymer electrolyte according to claim 9 , wherein the cationic-functionalized polymer has a structure satisfying a Formula IXC, XC, or XD

11. The polymer electrolyte according to claim 1 , wherein the cationic-functionalized polymer has a structure satisfying a Formula XIA or XIB

wherein:

R 5 is aliphatic;

m is two or more up to the number of monomeric subunits coupled to form a particular polymeric species;

n of Formulas XIA and/or XIB is from 1 to at least m;

x is 0 to 0.99; and

r is from 0 to 4.

12. The polymer electrolyte of claim 1 , wherein the cationic-functionalized polymer is crosslinked.

13. The polymer electrolyte of claim 1 , wherein the polyacid is a diacid having structure satisfying a Formula XII or XIII

wherein R 1 and R 2 independently are H, F, OH, aliphatic, alkoxy, or aromatic; and k is an integer selected from 1 to 20.

14. The polymer electrolyte of claim 1 , wherein the polyacid dopant is present in an amount such that a mole of acid per cationic functional group is 1 to 15.

15. The polymer electrolyte of claim 1 , comprising

wherein each R independently is CH 2 , (CH 2 ) 3 , CF 2 , C(Me)(OH), or any combination thereof; n is an integer selected from one or higher; and x ranges from 0 to 0.99.

16. A fuel cell, comprising:

an anode;

a cathode; and

a polymer electrolyte comprising a cationic-functionalized polymer comprising a polymer and least one cationic functional group, wherein the polymer is selected from a polyaryl polymer, a polyarylamide, a polyimide, a polystyrene, a polysulfone, a polyether, a polyether sulfone, a polyketone, a polyetherketone, a polyarylether, a polyolefin, or a polynitrile, and wherein the at least one cationic functional group (CFG) is selected from ammonium [—NH 3 +

imidazolium

guanidinium

phosphazenium

sulfonium [sulfonium

oxonium

piperidinium

pyridinium

quinolinium

and phosphonium

wherein R 1 , R 2 , and R 3 are independently hydrogen, aliphatic, aryl, or heteroaryl; and a polyacid dopant having a structure satisfying a formula R—[PO(OH) 2 ] n or R—[S(O) 2 OH] n wherein R comprises an aliphatic group or an aromatic group and n is an integer selected from 2 to 4.

17. The fuel cell of claim 16 , further comprising a phosphonated poly(pentafluorostyrene) polymer.

18. A polymer electrolyte, comprising:

a cationic-functionalized polymer comprising a polymer and least one cationic functional group, wherein the polymer is selected from a polyaryl polymer, a polyarylamide, a polyimide, a polystyrene, a polysulfone, a polyether, a polyether sulfone, a polyketone, a polyetherketone, a polyarylether, a polyolefin, or a polynitrile, and wherein the at least one cationic functional group (CFG) is selected from ammonium [—NH 3 + ,

imidazolium

guanidinium

phosphazenium

sulfonium [sulfonium

oxonium

piperidinium

pyridinium

quinolinium

and phosphonium

wherein R 1 , R 2 , and R 3 are independently hydrogen, aliphatic, aryl, or heteroaryl; and

a polyacid dopant having a structure satisfying a formula R—[PO(OH) 2 ] n or R—[S(O) 2 OH] n wherein R comprises an aliphatic or aromatic group and n is an integer selected from 2 to 4; and wherein the polymer electrolyte provides an ion conductivity of 10 mS/cm or greater at temperatures above 120° C.