The present disclosure relates to cross-linked polyelectrolytes comprising polyelectrolyte, and composite materials comprising said cross-linked polyelectrolytes. The present disclosure further relates to membrane electrode assemblies comprising the cross-linked polyelectrolytes and composites of the disclosure, and electrochemical devices comprising the disclosed membrane electrode assemblies.

The present disclosure relates to cross-linked polyelectrolytes comprising polyelectrolyte, and composite materials comprising said cross-linked polyelectrolytes. The present disclosure further relates to membrane electrode assemblies comprising the cross-linked polyelectrolytes and composites of the disclosure, and electrochemical devices comprising the disclosed membrane electrode assemblies.

A solid electrolyte includes an amorphous silica network and phosphoric acid. The phosphoric acid is contained in the amorphous silica network, and is typically in molecular form. The ratio of silicon to phosphorus in the solid electrolyte is about 1:4, and the silicon is in a four-coordinated state. The solid electrolyte is in the form of a dried (e.g., anhydrous) gel. The solid electrolyte may be used in a fuel cell membrane. Preparing the solid electrolyte includes reacting phosphoric acid in the liquid state with tetrachloride compound including silicon and a displaceable ligand to yield a fluid suspension, heating the fluid suspension to yield a liquid electrolyte comprising a particulate solid, separating the particulate solid from the liquid electrolyte, combining the particulate solid with water to yield a homogenous solution, forming a gel from the homogeneous solution, and removing water from the gel to yield the solid electrolyte.

A solid electrolyte includes an amorphous silica network and phosphoric acid. The phosphoric acid is contained in the amorphous silica network, and is typically in molecular form. The ratio of silicon to phosphorus in the solid electrolyte is about 1:4, and the silicon is in a four-coordinated state. The solid electrolyte is in the form of a dried (e.g., anhydrous) gel. The solid electrolyte may be used in a fuel cell membrane. Preparing the solid electrolyte includes reacting phosphoric acid in the liquid state with tetrachloride compound including silicon and a displaceable ligand to yield a fluid suspension, heating the fluid suspension to yield a liquid electrolyte comprising a particulate solid, separating the particulate solid from the liquid electrolyte, combining the particulate solid with water to yield a homogenous solution, forming a gel from the homogeneous solution, and removing water from the gel to yield the solid electrolyte.

A sulfonated polyphosphazene copolymer proton exchange membrane material, and a method for preparing such membrane includes a macromolecule initiator as bromo polyphosphazene is subjected to atom transfer radical polymerization with styrene, yielding a graft copolymer, which is hydrazinolyzed with hydrazine hydrate resulting in a copolymer including a hydroxyl group. The copolymer is reacted with 1,4-butane sultone to yield a sulfonated copolymer finally. The polymer is cross-linked with 2,6-di(hydroxymethyl)-4-methyl phenol (BHMP) as a cross linking agent in the presence of methyl sulfonic acid, yielding cross-linked proton exchange membrane. Such cross-linked graft copolymer membrane has high proton conductivity, low methanol hindrance, and low cost, and has ideal effect when applied in fuel cells as proton exchange membrane material.

A sulfonated polyphosphazene copolymer proton exchange membrane material, and a method for preparing such membrane includes a macromolecule initiator as bromo polyphosphazene is subjected to atom transfer radical polymerization with styrene, yielding a graft copolymer, which is hydrazinolyzed with hydrazine hydrate resulting in a copolymer including a hydroxyl group. The copolymer is reacted with 1,4-butane sultone to yield a sulfonated copolymer finally. The polymer is cross-linked with 2,6-di(hydroxymethyl)-4-methyl phenol (BHMP) as a cross linking agent in the presence of methyl sulfonic acid, yielding cross-linked proton exchange membrane. Such cross-linked graft copolymer membrane has high proton conductivity, low methanol hindrance, and low cost, and has ideal effect when applied in fuel cells as proton exchange membrane material.

Disclosed is a composite electrolyte membrane comprising a microporous polymer substrate and a sulfonated polymer electrolyte. The composite electrolyte membrane comprises: a first polymer electrolyte layer formed of a first non-fluorinated or partially-fluorinated sulfonated polymer electrolyte; a non-fluorinated or partially-fluorinated microporous polymer substrate stacked on the first polymer electrolyte layer, wherein pores of the microporous polymer substrate are impregnated with a second non-fluorinated or partially-fluorinated sulfonated polymer electrolyte, and the first polymer electrolyte and the second polymer electrolyte are entangled with each other on an interface thereof; and a third polymer electrolyte layer formed on the microporous polymer substrate impregnated with the second polymer electrolyte by a third non-fluorinated or partially-fluorinated sulfonated polymer electrolyte, wherein the second polymer electrolyte and the third polymer electrolyte are entangled with each other on an interface thereof. A method for manufacturing the composite electrolyte membrane, and a membrane-electrode assembly (MEA) and a fuel cell comprising the composite electrolyte membrane are also disclosed.

Disclosed is a composite electrolyte membrane comprising a microporous polymer substrate and a sulfonated polymer electrolyte. The composite electrolyte membrane comprises: a first polymer electrolyte layer formed of a first non-fluorinated or partially-fluorinated sulfonated polymer electrolyte; a non-fluorinated or partially-fluorinated microporous polymer substrate stacked on the first polymer electrolyte layer, wherein pores of the microporous polymer substrate are impregnated with a second non-fluorinated or partially-fluorinated sulfonated polymer electrolyte, and the first polymer electrolyte and the second polymer electrolyte are entangled with each other on an interface thereof; and a third polymer electrolyte layer formed on the microporous polymer substrate impregnated with the second polymer electrolyte by a third non-fluorinated or partially-fluorinated sulfonated polymer electrolyte, wherein the second polymer electrolyte and the third polymer electrolyte are entangled with each other on an interface thereof. A method for manufacturing the composite electrolyte membrane, and a membrane-electrode assembly (MEA) and a fuel cell comprising the composite electrolyte membrane are also disclosed.

Described herein is method of making a multifunctional compound by starting with a H(OR).sub.nP(O)(OR.sub.h.sup.1).sub.2 and performed a series of reactions to form a functionalized phosphorous compound such as CF.sub.2CFCFY.sup.2(OR).sub.nP(O)(OQ).sub.2(VIIA) CF.sub.2X.sup.3CFCF(OR).sub.nP(O)(OQ).sub.2(VIIB), or CF.sub.2X.sup.3CHFC(O)(OR).sub.nP(O)(OH).sub.2(VIB) Where: R is a C1-C4 alkenyl group; X.sup.3 is F or (OR).sub.nP(O)(OQ).sub.2; n is 0 or 1; Y.sup.2 is F, Cl, Br, H, or a fluoroalkyl group comprising 1 to 3 carbon atoms, wherein the fluoroalkyl group optionally comprises at least one of an ether linkage, Cl, Br, or I; and Q is an alkyl group having 1 to 6 carbon atoms and optionally comprising at least one catenated ether linkage, Si(CH.sub.3).sub.3, Si(CH.sub.2CH.sub.3).sub.3, H, a metallic cation, or a quaternary ammonium cation can be disposed on a metal surface. Such compounds may be used in generating ionomeric polymers and/or applied onto metal substrates.

Described herein is method of making a multifunctional compound by starting with a H(OR).sub.nP(O)(OR.sub.h.sup.1).sub.2 and performed a series of reactions to form a functionalized phosphorous compound such as CF.sub.2CFCFY.sup.2(OR).sub.nP(O)(OQ).sub.2(VIIA) CF.sub.2X.sup.3CFCF(OR).sub.nP(O)(OQ).sub.2(VIIB), or CF.sub.2X.sup.3CHFC(O)(OR).sub.nP(O)(OH).sub.2(VIB) Where: R is a C1-C4 alkenyl group; X.sup.3 is F or (OR).sub.nP(O)(OQ).sub.2; n is 0 or 1; Y.sup.2 is F, Cl, Br, H, or a fluoroalkyl group comprising 1 to 3 carbon atoms, wherein the fluoroalkyl group optionally comprises at least one of an ether linkage, Cl, Br, or I; and Q is an alkyl group having 1 to 6 carbon atoms and optionally comprising at least one catenated ether linkage, Si(CH.sub.3).sub.3, Si(CH.sub.2CH.sub.3).sub.3, H, a metallic cation, or a quaternary ammonium cation can be disposed on a metal surface. Such compounds may be used in generating ionomeric polymers and/or applied onto metal substrates.