Conjugated acid proton exchange polymers and methods for manufacturing and using conjugated acid proton exchange polymers.

Description

1 / 70 Conjugated acid proton exchange polymers and methods for manufacturing and using proton exchange polymers. Conjugate acids RELATED ORDERS

[001] This application claims priority to U.S. Provisional Patent Application No. 63 / 457,873, filed April 7, 2023, the contents of which are incorporated by reference in their entirety. FUNDAMENTAL INFORMATION

[002] In electrochemical cells, such as hydrogen fuel cells and water electrolysis systems, proton exchange membranes (PEMs) are used to selectively transport protons. Proton exchange membranes (PEMs) are semipermeable membranes that transport protons (H+) and are impermeable to gases. PEMs are generally composed of a porous structure with highly acidic functional groups. For example, polyfluorosulfonic acid-based PEMs, such as Nation™ (The Chemours Company, Wilmington, Delaware) and Aquivion® (Solvay SA Corporation, Brussels, Belgium), contain a porous poly(tetrafluoroethylene) (PTFE) structure with pendant sulfonic acid side groups. The readily dissociable sulfonic acid groups serve as proton transport agents in the membrane. In hydrogen fuel cells, hydrogen gas (H2) separates at the anode into Petition 870250102744, dated 10 / 11 / 2025, page 9 / 84 2 / 70 protons (H+) and electrons. The protons pass through an EMP and combine with oxygen gas (O2) at a cathode to produce water, while the electrons flow through an external circuit to produce electricity. In water electrolysis systems, electricity splits the water at the anode into oxygen gas (O2) and protons (H+). The protons pass through the EMP and combine with electrons at the cathode to produce hydrogen gas (H2).

[003] A membrane electrode array (MEA) may include a PEM positioned between a first catalyst layer and a second catalyst layer. The catalyst layers are electrically conductive electrodes (anode and cathode) with embedded electrochemical catalysts, such as metals, metal alloys, or metal oxides. The catalysts may be bonded to a solid catalyst support, which is usually an electrically conductive, high-surface-area carbon (e.g., graphite or graphene). Electrochemical catalysts reduce the activation energy required to carry out electrochemical reactions at the electrodes, such as the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in water electrolysis applications, and the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) in fuel cell applications.

[004] In some applications, the catalyst layer includes a supported catalyst mixed with an ionomer, Petition 870250102744, dated 10 / 11 / 2025, page 10 / 84 3 / 70 an ion-conducting polymer. The ionomer binds the catalysts within the electrode, bonds the catalyst layer to the PEM, and provides a pathway for cations (e.g., protons), thus improving cation conductivity. In some MEAs, the catalyst layers are formed separately from the PEM and layered over the PEM in the MEA stack. In other MEAs, the catalyst layers are coated onto the PEM to form catalyst-coated membranes (CCMs).

[005] Water electrolysis and fuel cell applications involve strong oxidation-reduction chemistries under high-temperature, acidic ambient conditions. Therefore, PEMs and ionomers, as well as the molecular functional groups responsible for proton transport properties, must remain robust under the severe reaction conditions of redox stress. However, conventional polymers used in PEMs and as ionomers, such as Nation™ and Aquivion®, primarily contain sulfonic acid functional groups as proton transport agents. Sulfonic acid functional groups have limited capacity to withstand the redox stress of electrochemical operations, mainly due to the intrinsic physicochemical properties of sulfur. Furthermore, sulfonic acid groups participate in secondary redox reactions that promote metal catalyst poisoning. Petition 870250102744, dated 10 / 11 / 2025, page 11 / 84 4 / 70 platinum and the depolymerization of polymer matrices. BRIEF DESCRIPTION OF THE DRAWINGS

[006] The attached drawings illustrate various embodiments and form part of the specification. The embodiments illustrated are merely examples and do not limit the scope of the description. Throughout the drawings, identical or similar reference numbers designate identical or similar elements.

[007] FIG. 1 shows an illustrative reaction scheme for producing a proton-conducting polybenzimidazolium (PBI+) polymer ionically linked to a tetrafluoroborate counteranion.

[008] FIG. 2 shows another illustrative reaction scheme for the production of a PBI+ polymer ionically linked to a non-coordination tetrafluoroborate counter-anion.

[009] FIG. 3 shows an illustrative reaction scheme for the production of a PBI+ polymer ionically linked to any of several non-coordinated metal fluoride counter-anions.

[0010] FIG. 4 shows another illustrative reaction scheme for the production of a PBI+ polymer ionically linked to a non-coordinating tetrafluoroborate counter-anion.

[0011] FIG. 5 shows an illustrative system of Petition 870250102744, dated 10 / 11 / 2025, page 12 / 84 5 / 70 electrolysis of water by a proton exchange membrane incorporating PEMs and / or conjugated acid proton exchange polymer ionomers.

[0012] FIG. 6 shows an illustrative proton exchange membrane fuel cell that includes PEMs and / or conjugated acid proton exchange polymer ionomers. DETAILED DESCRIPTION

[0013] This document describes conjugated acid proton exchange polymers and methods for manufacturing and using conjugated acid proton exchange polymers by post-polymerization functional modification of basic aromatic polymers.

[0014] Basic aromatic polymers include basic aromatic units (e.g., aryl groups and / or heteroaryl groups) in the main chain and / or side chains or side groups. Examples of basic aromatic polymers include, but are not limited to, polybenzimidazole (PBI) polymers and polyaniline (PANI) polymers, among many others. The basic aromatic units are weakly basic and react with a strong acid in an acid-base reaction to form an acidic aromatic unit that is ionically linked to a counter-anion. The acidic aromatic unit is a conjugate acid of the basic aromatic unit. In some examples, the counter-anion is the conjugate base of the strong acid, although the ion-exchange group may be modified. Petition 870250102744, dated 10 / 11 / 2025, p. 13 / 84 6 / 70 depending on the application and desired properties. The acidic aromatic unit readily dissociates in an aqueous environment to form a balanced mixture that includes hydrated protons (HsO+). Thus, readily dissociable acidic aromatic units can serve as proton transport agents.

[0015] The conjugated acid proton exchange polymers described herein can be used in electrochemical cell applications, such as in PEMs, ionomers, catalyst layers, and membrane electrode arrays (MEAs), as well as in other applications. The counter-anion (conjugated base) is a non-coordinated ion that remains stable and passive under severe electrochemical reaction conditions, does not poison electrochemical catalysts by reacting with metal catalysts, and does not participate in secondary depolymerization reactions. Thus, ionomers and PEMs based on conjugated acid proton exchange polymers, as described in this document, reduce or eliminate catalyst poisoning compared to conventional ionomers and polymers, including sulfonic acid-functionalized polymers such as Nation®.

[0016] Several definitions will now be provided to aid in understanding various aspects of the present description. As used in this document, each term or expression, for example, alkyl, m, n, etc., when used Petition 870250102744, dated 10 / 11 / 2025, page 14 / 84 7 / 70, when used more than once, is intended to be independent of its definition elsewhere in this description. In case of conflict with any patent application or patent incorporated herein by reference, this specification, including the definitions, shall prevail.

[0017] As used in this document, “polymer” refers to a substance comprising polymer molecules of the same or different polymer species, including a mixture of polymer molecules of the same polymer species that may differ from other polymer molecules within the same sample in chain length and / or specific structural arrangement (e.g., irregularities in the orientation of monomer units, end groups, and / or the locations and / or lengths of any side chains or side groups). “Polymer” includes homopolymers, copolymers, terpolymers, interpolymers, and so forth.

[0018] As used in this document, “polymer molecule” or “macromolecule” refers to a molecule of high relative molecular weight whose structure comprises a relatively large repetition of units (e.g., about 100 or more monomer units) derived, actually or conceptually, from molecules of low relative molecular weight (e.g., monomer molecules).

[0019] As used in this document, Petition 870250102744, dated 10 / 11 / 2025, page 15 / 84 8 / 70 “Polymerization” refers to the process of converting a monomer, or a mixture of monomers, into a polymer.

[0020] As used in this document, “oligomer” refers to a substance composed of oligomer molecules.

[0021] As used in this document, “oligomer molecule” refers to a molecule of intermediate relative molecular mass, whose structure comprises a relatively small repetition of units (e.g., about 5 to about 100 monomer units) derived, actually or conceptually, from molecules of lower relative molecular mass (e.g., monomer molecules).

[0022] As used in this document, “oligomerization” refers to the process of converting a monomer or a mixture of monomers into an oligomer.

[0023] The principles, concepts, and resources described in this document with reference to polymers, polymer molecules, and polymerization apply equally to oligomers, oligomer molecules, and oligomerization, respectively. Therefore, any and all uses of the terms polymer, polymer molecule, and polymerization contained herein may be replaced by the terms oligomer, oligomer molecule, and oligomerization, respectively, without departing from the scope of the description contained herein.

[0024] As used in this document, “ionomer” is Petition 870250102744, dated 10 / 11 / 2025, page 16 / 84 9 / 70 refers to a polymer composed of ionomer molecules.

[0025] As used in this document, “ionomer molecule” refers to a polymer molecule in which a small but relatively significant proportion of the constitutional units have ionizable or ionic pendant groups (including the ion-exchange groups described in this document), or both. In general, no more than approximately 15 molar percent of the constitutional units have ionizable or ionic pendant groups.

[0026] As used in this document, “monomer” refers to a substance composed of monomer molecules.

[0027] As used in this document, “monomer molecule” refers to a molecule that can undergo polymerization or oligomerization to form a polymer molecule or an oligomer molecule. A monomer molecule contributes constituent units to the essential structure of a polymer molecule or an oligomer molecule.

[0028] As used in this document, “copolymer” refers to a polymer derived from more than one type of monomer.

[0029] As used in this document, “constitutional unit” refers to an atom or group of atoms (with dangling atoms or groups, if any) that comprises a part of the structure of a polymer molecule (or Petition 870250102744, dated 10 / 11 / 2025, page 17 / 84 10 / 70 oligomer molecule, block or chain).

[0030] As used in this document, “repeating unit” refers to the constitutional unit whose repetition constitutes a polymer molecule (or oligomer molecule, block or chain).

[0031] As used in this document, “monomer unit” refers to the largest constitutional unit contributed by a single monomer molecule to the structure of a polymer molecule or an oligomer molecule.

[0032] As used in this document, “block” refers to a portion of a polymer molecule (or oligomer molecule) comprising many constitutional units and having at least one feature that is not present in adjacent portions.

[0033] As used in this document, “chain” refers to all or part of a polymer molecule (or oligomer molecule or block), comprising a linear or branched sequence of constitutional units between two boundary constitutional units, each of which may be an end group, a branching point, or an otherwise designated feature of the polymer molecule.

[0034] As used in this document, “main chain” or “main structure” refers to the chain of Petition 870250102744, dated 10 / 11 / 2025, p. 18 / 84 11 / 70 a polymer molecule to which all other chains (long, short, or both) can be considered attached (e.g., a side chain).

[0035] As used in this document, “side chain” refers to an oligomeric (short chain) or polymeric (long chain) branch of the main chain of a polymer molecule.

[0036] As used in this document, “side group” or “pendant group” refers to a branch, neither oligomeric nor polymeric, of a chain (e.g., a main chain).

[0037] The principles, concepts, and resources described here with respect to side chains apply equally to side groups. Therefore, any use of the term side chain can be replaced by the term side group without departing from the scope of the description contained herein.

[0038] As used in this document, “crosslinking refers to a small region in a polymer molecule from which at least four chains emanate. A crosslink is usually formed by reactions involving sites or groups on existing polymer molecules or by interactions between existing polymer molecules.

[0039] The term “crosslinked” refers to the state in which polymer molecules that were previously polymer molecules Petition 870250102744, dated 10 / 11 / 2025, p. 19 / 84 12 / 70 separate tubes are connected to each other at points that are not their ends.

[0040] As used in this document, a “catalyst particle” refers to a particle in “black” or pure form (e.g., excluding any catalyst support to which the catalyst particle may be attached and excluding any catalyst additives) that increases the rate of a reaction without modifying the overall change in standard Gibbs free energy in the reaction. A catalyst particle may be an individual molecule (including, but not limited to, a monomer molecule), a group of molecules, a crystal structure (e.g., as in a metal oxide), a polymer molecule, or an oligomer molecule. A catalyst particle may have any suitable size and shape, such as a microparticle, a nanoparticle, or a nanotube.A catalyst particle may include, for example, a metal, a metal alloy, a metal oxide, a metal halide (e.g., a metal chloride), or a compound that includes at least one metal, a metal alloy, a metal oxide, or a metal halide.

[0041] As used in this document, an “electrocatalyst particle” or “electrochemical catalyst particle” refers to a catalyst particle that reduces the activation energy required to carry out electrochemical reactions and / or increases the rate of reactions. Petition 870250102744, dated 10 / 11 / 2025, page 20 / 84 13 / 70 electrochemical, such as OER, HER, HOR and / or ORR.Suitable electrocatalyst particles may include, without limitation, metals such as platinum group metals (PGMs) (e.g., platinum, palladium, iridium, ruthenium, osmium, and rhodium), transition metals (e.g., silver, gold, cobalt, copper, iron, nickel, rhenium, and mercury), and post-transition metals (e.g., bismuth and tin), metal alloys (e.g., PGM transition metal-based alloys and platinum-ruthenium-based alloys), metal oxides (e.g., PGM oxides such as iridium(IV) oxide, ruthenium(IV) oxide, iridium-ruthenium oxide, platinum(IV) oxide, magnesium oxide, and cerium(IV) oxide), metal halides (e.g., platinum chloride). (IV), iridium (III) chloride, platinum (IV) bromide, iridium (III) bromide) and / or metal compounds, metal alloys, metal oxides and / or metal halides.

[0042] As used in this document, a “catalyst carrier” refers to a substance, excluding a catalyst particle, that can be used to support catalyst particles (e.g., a substance or material to which catalyst particles can be attached or on which catalyst particles can be supported). Examples of catalyst carriers include, Petition 870250102744, dated 10 / 11 / 2025, page 21 / 84 14 / 70 without limitation, carbon-based materials (for example, carbon black, graphite, carbon nanotubes, graphene and / or boron-functionalized carbon materials described in this document), titanium dioxide, Sb-doped SnO2 nanoparticles, tin-doped indium oxide (ITO) and / or the ion-exchange modified catalyst supports described in International Patent Application No. PCT / US2022 / 046105, filed on October 7, 2022, the contents of which are incorporated herein by reference in their entirety.

[0043] As used in this document, a “catalyst” refers to a catalyst particle, as well as a catalyst particle together with a catalyst carrier on which the catalyst particle is supported or to which the catalyst particle is attached. A catalyst may also include catalyst additives, such as promoters (such as, but not limited to, metalloids).

[0044] As used in this document, an “electrocatalyst” or “electrochemical catalyst” refers to an electrocatalyst particle in “black” or pure form, as well as an electrocatalyst particle together with a catalyst carrier on which the electrocatalyst particle is supported or to which the catalyst particle is attached. An electrocatalyst may also include catalyst additives, such as promoters. Petition 870250102744, dated 10 / 11 / 2025, page 22 / 84 15 / 70

[0045] As used in this document, “metal” includes alkali metals, alkaline earth metals, transition metals, lanthanides, actinides, and post-transition metals.

[0046] As used in this document, “transition metals” refers to elements in the d-block of the periodic table (groups 3 to 12 inclusive).

[0047] As used in this document, “post-transition metals” refers to aluminum, gallium, indium, tin, thallium, lead, bismuth, and polonium.

[0048] As used in this document, “metalloids” refers to boron, silicon, germanium, arsenic, antimony, tellurium, and astatine.

[0049] As used in this document, “platinum group metals” or “PGMs” refers to platinum, palladium, iridium, ruthenium, osmium, and rhodium.

[0050] As used in this document, “aliphatic” compounds are saturated or unsaturated hydrocarbons, acyclic or cyclic, unbranched or branched, unsubstituted or wholly or partially substituted by one or more substituents or functional groups. As will be appreciated by someone with expertise in the field, the term “aliphatic” includes, but is not limited to, alkyl, alkenyl, and alkynyl. Illustrative aliphatic groups include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, Petition 870250102744, dated 10 / 11 / 2025, p. 23 / 84 16 / 70 sec-pentyl, isopentyl, tert-pentyl, n-hexyl and sechexyl.

[0051] As used in this document, the term “alkyl” has its common meaning in the art and may include saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups. A similar convention applies to other generic terms such as “alkenyl,” “alkynyl,” and the like. Furthermore, as used in this document, the terms “alkyl,” “alkenyl,” “alkynyl,” and the like encompass fully or partially substituted and unsubstituted groups.

[0052] In some embodiments, a straight or branched alkyl chain may have from 1 to 30 carbon atoms in its main chain and, in some cases, from 1 to 20 or less. In some embodiments, a straight or branched alkyl chain has from 1 to 10 carbon atoms in its main chain (e.g., C1-C10 for straight chain, C3-C10 for branched chain), has 6 or fewer carbon atoms, or has 4 or fewer carbon atoms. Cycloalkyls may have from 3 to 10 carbon atoms in their ring structure or, in some cases, from 3 to 5, 6, or 7 carbon atoms in the ring structure. Examples of non-cyclic alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, Petition 870250102744, dated 10 / 11 / 2025, p. 24 / 84 17 / 70 isobutyl, n-butyl, tert-butyl, n-pentyl, neopentyl, nhexyl, n-heptyl, n-octyl, n-decyl, n-undecyl and dodecyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclobutyl and cyclohexyl.

[0053] The terms alkenyl and alkynyl refer to unsaturated aliphatic groups analogous in length and possible substitution to the alkyl groups described above, but containing at least one double or triple bond, respectively. Alkenyl groups include, without limitation, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl and the like. Non-limiting examples of alkynyl groups include ethinyl, 2-propynyl (propargyl), 1-propynyl and the like.

[0054] The term heteroatom refers to any atom other than carbon. Non-limiting examples of heteroatoms include B, N, O, Al, Si, P, S, Ge, As, Se, and Sb. In some instances, a heteroatom is an atom selected from the group consisting of B, N, O, P, and S.

[0055] The term heteroalkyl refers to an alkyl group in which one or more hydrogen atoms bonded to any carbon of the alkyl group or one or more carbon atoms are replaced by a heteroatom. Examples of heteroalkyl groups include, without limitation, methoxy, ethoxy, propoxy, isopropoxy, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, methoxymethyl and cyano groups. Petition 870250102744, dated 10 / 11 / 2025, p. 25 / 84 18 / 70

[0056] The terms heteroalkenyl and heteroalkynyl refer to unsaturated aliphatic groups analogous in length and possible substitution to the heteroalkyl described above, but containing at least one double or triple bond, respectively.

[0057] The term aryl refers to unsubstituted or partially or fully substituted aromatic carbocyclic groups with a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings, wherein at least one ring of the aryl group is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthrile). That is, at least one ring of an aryl group has a conjugated Pi electron system, while other rings of the aryl group may be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, and / or heterocycles. Carbocyclic aryl groups refer to aryl groups in which the atoms of the aromatic ring are carbon atoms. Carbocyclic aryl groups include monocyclic aryl groups and polycyclic or fused compounds (i.e., two or more atoms from adjacent rings are common to two adjacent rings), such as the naphthyl group.Aryl groups are not limited to benzene and its derivatives, but can have any suitable number of atoms in the ring. Examples of aryl groups include, without limitation, phenyl, naphthyl, tetrahydronaphthyl, anyl, indanyl, and... Petition 870250102744, dated 10 / 11 / 2025, p. 26 / 84 19 / 70 indemnity.

[0058] The term heteroaryl refers to aryl groups that contain at least one heteroatom as a ring atom (e.g., heteroaromatic groups), such as a heterocyclic group. Non-limiting examples of heteroaryl groups include, without limitation, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, and isoquinolinyl. Heteroaryl groups may be referred to as A-heteroaryl, where A is the symbol of the heteroatom element. For example, N-heteroaryl refers to an aryl group that includes at least one nitrogen atom as a ring atom.

[0059] The terms alkoxy or alkoxy, as used in this document, refer to an alkyl group with an oxygen radical attached to it, and has the general formula RO. Examples of alkoxy groups include, without limitation, methoxy, ethoxy, propyloxy and tert-butoxy groups.

[0060] The term aryloxy refers to an aryl group with an oxygen radical attached to it. An example of an alkoxy group includes, without limitation, a phenoxy group.

[0061] Any of the above groups may be optionally substituted, in whole or in part. Examples of substituents include, without limitation, aliphatic, alicyclic, heteroaliphatic, heteroalicyclic, Petition 870250102744, dated 10 / 11 / 2025, page 27 / 84 20 / 70 halogenium, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, amine, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, alkyloxycarbonyl, silyl, ether, alkylthio, heteroalkylthio, heteroarylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocycle, aromatic or heteroaromatic portions, -CF3, -CN, aryl, aryloxy, perhaloalkoxy, aralkoxy, heteroaryl, heteroaryloxy, heteroarylkyl, heteroalkoxy, azido, amino, haleto, alkylthio, oxo, acylalkyl, carboxy esters, -carboxamido, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxylaryl, arylamino, aralkylamino, alkylsulfonyl, -carboxamidoalkylaryl, carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxyl-, aminocarboxamidoalkyl-, cyano, alkoxyalkyl, peraloalkyl, arylalkylaxyalkyl, (eg, SO4(R')2), a phosphate (e.g., PO4(R')3), a silane (e.g., Si(R')4), a urethane (e.g., R'O(CO)NHr') and the like. Furthermore, substituents may be selected from —OH, —NO2, —CN, —NCO, —CF3, —CH2CF3, —CHCh, —CH2ORx, —CH2CH2ORX, —CH2N(Rx)2, —CH2SO2CH3, —C(O)Rx, —O2(Rx), —CON(Rx)2, —OC(O)Rx, —C(O)OC(O)Rx, —OCO2RX, —OCON(Rx)2, —N(Rx)2, —S(O)2Rx, —OCO2RX, —NRx(CO)Rx, —NRx(CO)N(Rx)2, wherein each occurrence of Rx independently includes, but is not limited to, hydrogen, aliphatic, alicyclic. Petition 870250102744, dated 10 / 11 / 2025, page 28 / 84 21 / 70 heteroaliphatic, heteroal cyclic, aryl, heteroaryl, alkylaryl or alkyl heteroaryl, wherein any of the aliphatic, alicyclic, heteroaliphatic, heteroal cyclic, alkylaryl or alkyl heteroaryl substituents described above and in this document may be wholly or partially substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and wherein any of the aryl or heteroaryl substituents described above and in this document may be wholly or partially substituted or unsubstituted.

[0062] Polytetrafluoroethylene (PTFE) polymers are a class of polymers composed of tetrafluoroethylene polymer molecules and their derivatives, and are produced by the polymerization of tetrafluoroethylene. PTFE polymer molecules have a carbon backbone with two fluorine atoms bonded to each carbon, and their derivatives.

[0063] Polychlorotrifluoroethylene (PCTFE) polymers are derived from PTFE and are homopolymers of chlorotrifluoroethylene (CTFE) with the molecular formula (CF2CCIF)ne and its derivatives. PCTFE is similar to PTFE (such as Teflon), except that PCTFE contains a chlorine atom in each repeating unit. The presence of this chlorine atom makes PCTFE a unique thermoplastic polymer with many applications. However, PCTFE has a hydrophobic back chain and is not ion-conductive, and Petition 870250102744, dated 10 / 11 / 2025, page 29 / 84 22 / 70, therefore, is not suitable for electrochemical applications. PCTFE polymer derivatives include substituent groups (e.g., side chains or side groups) in place of chlorine atoms. PCTFE derivatives may be wholly or partially substituted. PCTFE polymer derivatives include, without limitation, modified and functionalized PCTFE polymers, including any of the modified or functionalized PCTFE polymers (e.g., acid-functionalized and ion-exchange functionalized PCTFE polymers) described in U.S. Provisional Application No. 63 / 532,262, filed August 11, 2023, which is incorporated by reference in its entirety.

[0064] Sulfonic acid-functionalized PTFE polymers are derived from PTFE polymers and have a PTFE back chain and a side chain or side group with one or more pendant sulfonic acid groups. In some examples, the side chain is a long side chain (LSC) with at least two ether linkages and four or more polyfluorinated carbon units (e.g., -CF2- and / or -CF3). In other examples, the side chain is a short side chain (SSC) with one ether linkage and two polyfluorinated carbon units. In other examples, the side chain is an intermediate side chain (MSC) with one ether linkage and four polyfluorinated carbon units. Petition 870250102744, dated 10 / 11 / 2025, p. 30 / 84 23 / 70 In some examples, a sulfonic acid-functionalized PTFE polymer has the general formula [(CF2CF2)m(CFACF2)n], where A is a side chain comprising one or more pendant sulfonic acid groups, and en and nex are positive and selected based on application, equivalent weight, molecular weight, etc. In some examples, m ranges from 4 to 7 and en is 1. In some examples, the A side chain is an LSC, MSC, or SSC. Examples of LSC sulfonic acid-functionalized PTFE polymers include, without limitation, the Nation™ series polymers (available from Chemours Company in various configurations and grades, including Nafion-H, Nation HP, Nation 117, Nation 115, Nation 212, Nation 211, Nation NE1035, Nation XL, etc.) and any combination, derivative, grade, or configuration thereof. Examples of PTFE polymers functionalized with SSC sulfonic acid include, but are not limited to, the Aquivion® series polymers (available from Solvay SA).in different configurations and grades, including Aquivion® E98-05, Aquivion® PW98, Aquivion® PW87S, etc.), Gore-Select® (available from WL Gore & Associates, Inc.), Flemion™ (available from Asahi Glass Company), PEMion+™ (available from Ionomr Innovations, Inc.) and any combination, derivative, grade or configuration thereof. Examples of PTFE polymers functionalized with MSC sulfonic acid include, without limitation, polymers produced by 3M™ Company. In some examples, a PTFE polymer is... Petition 870250102744, dated 10 / 11 / 2025, page 31 / 84 24 / 70 a copolymer comprising one or more repeating units. In some examples, a PTFE polymer may be doped and / or crosslinked with itself and / or with another polymer.

[0065] Sulfonic acid functionalized polymers include, without limitation, polyfluorosulfonic acid (PFSA) polymers and non-fluorinated sulfonic acid polymers. Examples of polyfluorosulfonic acid polymers include, among others, sulfonic acid functionalized PTFE polymers and sulfonic acid functionalized PCTFE polymers. Examples of non-fluorinated sulfonic acid polymers include, without limitation, poly(styrene sulfonic acid) polymers, sulfonated aromatic polymers (e.g., sulfonated poly(ether ketone) polymers (SPEEK), sulfonated poly(aryl ether sulfone) polymers (SPAES), sulfonated poly(arylene ether ketone) polymers (SPAEK), sulfonated polysulfone polymers (SPSF), sulfonated polyimide polymers (SPI) and sulfonated polystyrene (SPS), sulfonated polyphenylene and any other sulfonated polymer, including sulfonated derivatives of polymers described in this document.

[0066] Polystyrene polymers are polymers composed of polystyrene polymer molecules. Polystyrene polymer molecules have a unit of Petition 870250102744, dated 10 / 11 / 2025, page 32 / 84 25 / 70 repeat that includes alternating carbon centers linked to a phenyl group.Examples of polystyrene polymers include, without limitation, polystyrene, poly(styrene sulfonic acid) (e.g., styrene sulfonic acid), poly(4-styrenesulfonic acid)), polyhalostrene, poly(3-trifluoromethylstyrene), poly(4-acetoxystyrene), poly(4-allylstyrene), poly(4-cyanostyrene), poly(4-dimethylsilylstyrene), poly(4-hydroxystyrene), poly(alpha-methylstyrene), poly(4-methylstyrene), poly(4-methoxystyrene), poly(4-[tert-butoxycarbonyl]oxystyrene), poly(4-tert-butylstyrene), poly(4-[N,N-di(trimethylsilyl)aminomethyl]styrene), poly(4-vinylbenzoic acid), n-butyl poly(4-vinylbenzoate), tert-butyl poly(4-vinylbenzoate), poly(4-vinylbenzoate 2-ethylhexyl), poly(methyl 4-vinylbenzoate), poly(vinylbenzyl chloride), poly(4-vinylbenzyl-N-methylphthalimide), poly(vinylcyclohexane) and derivatives of any of the above items (including substituted derivatives (e.g., poly(vinylbenzyl-N-methylphthalimide)).g., substituted (e.g., fluorinated) and / or branched derivatives). In some examples, a polystyrene polymer is a copolymer comprising one or more additional repeating units, which may or may not include a carbon center bonded to a phenyl group.

[0067] Aromatic polymers are polymers with one or Petition 870250102744, dated 10 / 11 / 2025, p. 33 / 84 26 / 70 more aromatic units in a main chain and / or in a side chain. An aromatic unit includes one or more aryl groups and / or heteroaryl groups. Examples of aromatic polymers include, without limitation, polystyrene polymers, polycarbonate polymers (polyphenylene polymers (e.g., poly(1,4-phenylene), poly(1,4-phenylene-ethylene), poly(1,3-phenylene-methylene), poly(p-phenylene vinylidene), poly(p-phenylene vinylene), poly(1,4-phenylene oxide), poly(1,4-phenylene sulfide)), poly(ether sulfone), polyaryletherketone polymers, polysulfone polymers, poly(ethylene terephthalate), aromatic polyester polymers, poly(oxy-1,4-phenylene carbonyl-1,4-phenylene), poly[(dimethylmethylene)bis(4,1-phenylene) carbonate], phenolic resins, poly[(ethylazanodyl)ethylene azanodyl-1,3-phenylene], polyoxydiphenylene pyromellitimide (Kapton®, manufactured by EI)du Pont de Nemours and Company), poly(imide ester) polymers, aromatic polyimide polymers, lignin and derivatives of any of the foregoing (including substituted (e.g., fluorinated) and / or branched), substituted (e.g., fluorinated) and / or branched derivatives).

[0068] Conjugated acid proton exchange polymers are synthesized by post-polymerization acid-base reactions between a basic aromatic polymer and an acid Petition 870250102744, dated 10 / 11 / 2025, page 34 / 84 27 / 70 to form a conjugate acid proton exchange polymer. Basic aromatic polymers are polymers that have a basic aromatic unit in a main chain and / or in a side chain of the polymer. A basic aromatic unit includes a basic aryl group and / or a basic heteroaryl group. The acid-base reaction converts the basic aromatic unit into an acidic aromatic unit by protonation of the basic aromatic unit. The acidic aromatic unit is the conjugate acid of the basic aromatic unit and has a formal positive charge due to the addition of the proton.

[0069] The resulting conjugated acid proton exchange polymer molecule includes an acidic aromatic unit in the main chain or side chain of the polymer molecule and a counter-anion ionically linked to the acidic aromatic unit. Conventional counter-anions, such as sulfates (derived from sulfuric acid), phosphates (derived from phosphoric acid and polyphosphoric acids), and halides, have substantial coordinating properties. These coordinating ions participate in catalyst poisoning reactions with metal catalysts and promote depolymerization reactions, thus reducing the yield and lifespan of a membrane electrode array (MEA). The size of the counter-anions, and more specifically the ionic potential (ratio of ion charge to ion radius) of the ions, also plays a role in Petition 870250102744, dated 10 / 11 / 2025, page 35 / 84 28 / 70 modulation of hydrogen bonding networks and water retention properties of proton exchange membranes.

[0070] To solve these problems, the counter-anion ionically bound to the acidic aromatic unit is a non-coordinating ion. Non-coordinating counter-anions remain stable and passive under severe electrochemical reaction conditions, do not poison catalysts when reacting with metal catalysts, and do not participate in secondary depolymerization reactions. Thus, in some examples, the counter-anion ionically bound to the acidic aromatic unit is the conjugate base of the acidic reagent used in the acid-base reaction, where the acidic reagent has a conjugate base that is a non-coordinating ion.In other examples, such as when the acidic reagent has a coordinating conjugate base, a subsequent fluorine treatment step is performed after the acid-base reaction to convert the counteranion into a non-coordinating counteranion (e.g., tetrafluoroborate or a metal fluoride), or a subsequent ion exchange step is performed after the acid-base reaction to exchange the counteranion for a non-coordinating counteranion (e.g., tetrafluoroborate).

[0071] The fluoride treatment stage and the ion exchange stage will be described in more detail below.

[0072] As mentioned, an aromatic unit Petition 870250102744, dated 10 / 11 / 2025, page 36 / 84 29 / 70 Basic includes a basic aryl group and / or a basic heteroaryl group. Basic aryl groups and basic heteroaryl groups have an amine with a single pair of electrons available to accept a proton from an acid, which makes the aryl group or the heteroaryl group, and therefore the aromatic unit, weakly basic. The amine may be on an aromatic ring of the aromatic unit, as in an N-heteroaryl group, or it may be in a substituent of the aromatic ring, as in an arylamine (e.g., aniline). The amine may be a primary amine, a secondary amine, or a tertiary amine.As used herein, a primary amine refers to a nitrogen atom bonded to a carbon atom and two hydrogen atoms (C-NH2), a secondary amine refers to a nitrogen atom bonded to two carbon atoms and one hydrogen atom (C-NH-C), and a tertiary amine refers to a nitrogen atom bonded to two carbon atoms and no hydrogen atoms (CN=C) or bonded to three carbon atoms (CN(-C)(-C)). A tertiary amine of a basic aromatic unit is a stronger base than a secondary amine of a basic aromatic unit, and a secondary amine of a basic aromatic unit is a stronger base than a primary amine of a basic aromatic unit.

[0073] Non-limiting examples of basic aromatic units include anilines (e.g., aniline, toluidines, Petition 870250102744, dated 10 / 11 / 2025, p. 37 / 84 30 / 70 xylidines, chloroanilines, aminobenzoic acids, nitroanilines, 2,5-diamino-1,4-phenylene), pyridines (e.g., 2,2'-bipyridine, 1,10-phenanthroline, 2,2';6'2-terpyridine, 4-chloro-[3,3-bipyridine]-5,5'-diyl; [2,3'-bipyridine]-4,5'-diyl; pyridine-4,2-diyl; pyridine-3,5-diyl; pyridine-2,4-diyl; pyridine-2,6-diyl), pyrazines (e.g., alkylpyrazines, such as 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,6-dimethylpyrazine, 2-ethyl-3-methylpyrazine, pyrazines methoxylated, such as 3-isobutyl-2-methoxypyrazine), imidazoles (for example 1,5-dihydrobenzo[1,2-d:4,5-cf]= diimidazol-2,6diyl; 4-phenyl-1H-imidazol-2,5-diyl; 4-phenyl-1H-imidazol5,2-diyl;1, 4-di(1-adamantil)pirazois, aminophenazona, metamizol), pyrimidines (for example 2,4dioxi pyrimidina, 2,4-dioxi-5-methyl pyrimidina, 2-oxi-4amino pyrimidina, 2,4-dioxi-6-carboxy-pyrimidina, 5-bromo2,4-dicloropirimidina,), piridazinas, tiazóis (por exemplo 6,6'-bi(1,3-benzotiazol)]-2,2'-diila, [2,2'-bi(1,3tiazol)]-4,4'-diil), imidazolinas, quinolinas (por exemplo quinolina-2,4-diil; [3,3'-biquinolina]-6,6'-diil), isoquinolinas, acridinas, quinoxilinas (por exemplo 3,3'; Petition 870250102744, of 10 / 11 / 2025, p. 38 / 84 31 / 70 diphenyl= [6,6'-biquinoxaline]-2,2'-diyl; 1 H,TH-[5,5'-bibenzimidazole]-2,2'-diyl), benzimidazoles, purines, indazoles, quinazolines, cinolines, tetrazines (e.g. 1,2,4,5-tetrazine-3,6-diyl), thiophenes (e.g. 3,4-dioctylthiophene-2,5-diyl; thiophene-2,5-diyl; thiophene-2,4-diyl) and derivatives of any of the foregoing.

[0074] Basic aromatic polymers include polymers produced by polymerization of monomeric units that include any basic aromatic units, or otherwise based on or incorporating any basic aromatic units.Non-limiting examples of basic aromatic polymers include polyaniline polymers (PANI) (including leucoesmeraldine, esmeraldine and pernigranilline forms), polypyrrole (PPy), polypyridine polymers (e.g. poly(2-isopropenylpyridine), poly(2,5-pyridine), poly(3,5-pyridine), poly(2-vinylpyridine), poly(4-vinylpyridine)), polypyrazine (e.g. poly(2-vinylpyrazine)), polyimidazole (e.g. poly(n-vinylimidazole), poly(4-vinylimidazole)), polypyrazole, polypyrimidine, polypyridazine (PPd), polythiazole, polyimidazolines, polyquinolines, polyisoquinolines, polyacridines, polyquinoxylines, polybenzimidazoles, polypurines, polynazoles, polyquinazolines, polycinolines, polytetrazines and polymers in which a unit Basic aromatic compounds are included in side chains or side groups. Petition 870250102744, dated 10 / 11 / 2025, page 39 / 84 32 / 70 (e.g., polypyridazines). g., poly(4-vinylpyridine) (PVP)).

[0075] The acidic reagent donates a proton to the basic aromatic unit to produce a conjugate acid of the basic aromatic unit. Any suitable acidic reagent can be used. In some examples, the acidic reagent has a conjugate base that is not coordinated, thus forming a counteranion that remains stable and passive under severe electrochemical reaction conditions, does not poison catalysts when reacting with metal catalysts, and does not participate in secondary depolymerization reactions. Non-limiting examples of suitable acids with a non-coordinated conjugate base include: fluoroboric acid (HBF4) (also known as tetrafluoroboric acid or hydrogen tetrafluoroborate ([H+][BF4]), which has the general structure: Phenyltrifluoroboric acid, which has the general structure: phenyl 1,4-di(trifluoro)boric acid, which has the general structure: Petition 870250102744, dated 10 / 11 / 2025, p. 40 / 84 33 / 70 Hexafluorophosphoric acid (HPFg), which has the following general structure: H® fluoroantimonic acid (also known as hydrogen hexafluoroantimonate (HFgSb)), which has the general structure: a sulfuric acid-boron trifluoride complex with the general structure: H® F H® FB^OSOB^-F is a complex of boron trifluoride and benzenesulfonic acid with the general structure: OFH® 11 lθ SOBF III a complex of boron trifluoride and benzene disulfonic acid with the general structure: Petition 870250102744, dated 10 / 11 / 2025, page 41 / 84 34 / 70 a complex of boron trifluoride and phosphoric acid with the general structure: FH® l® FBF H®F Ó Fu® I® । l® FBO-fj-OBF FOF .

[0076] It should be recognized that other acidic reagents with one or more fluoroboric acid groups are contemplated by this description and may be used in place of the acidic reagents described above. In some examples, the non-coordinating conjugate base / ions produced by the acidic reagent are tetrafluoroborate ([BF4-]), phenyl trifluoroborate (PhBFs-), hexafluorophosphate ([PFg-]), hexafluoroantimonate ([SbFg-]), benzenesulfonate-trifluoroborate (PhSOs (BF3)-) or sulfate-di(trifluoroborate) (SO4 (BF3) 2-).

[0077] In other examples, the acidic reagent has a conjugate base / counter-anion that is not coordinating. For example, sulfates, phosphates, and halides have substantial coordinating properties. As will be explained below, the coordinating counter-anion can be converted or replaced by a non-coordinating counter-anion in a fluoride treatment step or in an ion exchange step. Petition 870250102744, dated 10 / 11 / 2025, page 42 / 84 35 / 70

[0078] The acidic reagent in these examples may be an acid with the general formula HA, wherein A is a halide (e.g., F, Cl, or Br), HSO4, SO4, H2PO4, HPO4, PO4, or any polyphosphate ion derived from any polyphosphoric acid. Suitable examples of polyphosphoric acids include, but are not limited to, diphosphoric acid, triphosphoric acid, tetraphosphoric acid, and trimetaphosphoric acid. Non-limiting examples of HA acids include, without limitation, hydrofluoric acid (HF), hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid (H2SO4), fluorophosphoric acid (H2PO3F), phosphoric acid (H3PO4), or polyphosphoric acid.

[0079] The degree of protonation of the basic aromatic units can be adjusted to the desired levels by adjusting the molar ratio of the acidic reagent to the basic aromatic units of the polymer. For example, the molar ratio of the acidic reagent to the basic aromatic units can be 1:1, 1:2, 1:3, or any other suitable molar ratio. In some examples, the acidic reagent is the limiting reagent so that the aromatic units are not fully protonated. In other examples, the molar ratio of the acidic reagent to the basic aromatic unit is greater than 1:1 (e.g., 1.5:1, 2:1, 3:1, etc.) so that the basic aromatic units are fully protonated.

[0080] In an acid-base reaction, the basic aromatic unit is protonated by the acid and, therefore, is converted into a Petition 870250102744, dated 10 / 11 / 2025, page 43 / 84 36 / 70 Acidic aromatic unit. The acidic aromatic unit is the conjugate acid of the basic aromatic unit. Thus, the polymer molecule produced by the acid-base reaction is called a conjugate acid polymer molecule. The acid-base reaction is carried out under standard conditions and proceeds without the need for a catalyst. In the reaction, the amine of the basic aromatic unit is protonated when the amine's lone pair accepts the proton from the acid. Thus, the acidic aromatic unit is an N-protonated conjugate acid. When the basic aromatic unit is an imidazole unit or a pyridine unit, the acidic aromatic unit (N-protonated conjugate acid) may be called an imidazolium unit or a pyridinium unit, respectively. When the basic aromatic unit includes aniline, as in PAN I polymers, the acidic aromatic unit (N-protonated conjugate acid) is an ammonium derivative.The acidic aromatic unit has a positive charge on the protonated nitrogen and is counterbalanced by a counter-anion ionically bonded to the acidic aromatic unit. The counter-anion is the conjugate base of the acidic reagent.

[0081] When the acidic reagent is HBF4, HPF6, or fluoroantimonic acid, the counter-anion is a non-coordinating counter-anion (e.g., tetrafluoroborate ([BF4-]), hexafluorophosphate ([PFe-]), or hexafluoroantimonate ([SbFe-]), respectively). In this way, the conjugated acid proton exchange polymer can be used in applications Petition 870250102744, dated 10 / 11 / 2025, page 44 / 84 37 / 70 electrochemical.

[0082] In some examples, the ion exchange capacity (IEC) of the conjugated acid proton exchange polymer is increased by using an acidic reagent other than fluoroboric acid. In other examples, an acidic reagent with multiple fluoroboric acid groups (e.g., phenyl trifluoroboric acid, phenyl 1,4-di(trifluoro)boric acid, a sulfonic acid-BF3 complex, a phosphoric acid-BF3 complex) also acts as a crosslinking agent where each fluoroboric acid group reacts with different basic aromatic units of the same polymer molecule or of different polymer molecules.

[0083] Cross-linking in this manner increases the durability of the polymer and the IEC of the resulting conjugated acid proton exchange polymer.

[0084] When the acidic reagent has a conjugate base that is coordinated, a fluoride treatment step or an ion exchange step is performed on the intermediate conjugate acid proton exchange polymer to convert the counter-anion into a non-coordinating counter-anion or to exchange the counter-anion for a non-coordinating counter-anion.

[0085] For example, when the acidic reagent is hydrofluoric acid (HF), the acid-base reaction produces a conjugate acid proton exchange polymer intermediate in which the counter-anion is a fluoride ion (F-). Then, the following is carried out Petition 870250102744, dated 10 / 11 / 2025, page 45 / 84 38 / 70 a fluoride treatment step combining the intermediate conjugate acid proton exchange polymer with boron trifluoride (e.g., in the form of bf3(Et2O) etherate), a difluoro(phenyl)borane with one of the following general structures: or a metallic fluoride of general formula MFn, where M is beryllium (Be), aluminum (Al), bismuth (Bi), antimony (Sb), phosphorus (P), tin (Sn), zirconium (Zr), or titanium (Ti), and n corresponds to the valence of M. Boron trifluoride reacts with the fluoride anion via an addition reaction to form a non-coordinating tetrafluoroborate counter-anion, where M increases its oxidation state to add the fluoride anion. Similarly, a difluoro(phenyl)borane, as shown above, reacts with the fluoride ion via an addition reaction to form a non-coordinating trifluoro(phenyl)borate counter-anion. Metallic fluoride reacts with the fluoride ion via an addition reaction to form a non-coordinating metallic fluoride counter-anion with the general formula [MF(n+i)]₂, where M increases its oxidation state to add the fluoride ion. In Petition 870250102744, dated 10 / 11 / 2025, page 46 / 84 39 / 70 some examples, the non-coordinating metal fluoride counter-anion is beryllium fluoride (BF2), aluminum fluoride (AlF3), fluorinated bismuth (e.g., bismuth trifluoride (bismuth(III) fluoride), fluorinated antimony (e.g., antimony(III) trifluoride), fluorinated phosphorus (e.g., monofluorophosphate, difluorophosphate or hexafluorophosphate), fluorinated tin (tin(III) fluoride), fluorinated phosphorus (e.g., monofluorophosphate, difluorophosphate or hexafluorophosphate), monofluorophosphate, difluorophosphate or hexafluorophosphate), fluorinated tin (tin(II) fluoride, also known as stannous fluoride), fluorinated zirconium (e.g., zirconium(IV) fluoride) or fluorinated titanium (e.g., titanium trifluoride (titanium(III) fluoride) and titanium tetrafluoride (titanium(IV) fluoride)).

[0086] In some examples, the ion exchange capacity (IEC) of the conjugated acid proton exchange polymer is increased by using a difluoro(phenyl)borane in the fluorine treatment compared to boron trifluoride. In some examples, a difluoro(phenyl)borane with two difluoroboryl groups also acts as a crosslinking agent, where each difluoroboryl group crosslinks different aromatic units of the same polymer molecule or of different molecules.

[0087] Cross-linking in this way increases the Petition 870250102744, dated 10 / 11 / 2025, page 47 / 84 40 / 70 polymer durability and the IEC of the resulting conjugated acid proton exchange polymer.

[0088] In other examples, when the acidic reagent is an acid with the general formula HA described above, the acid-base reaction produces an intermediate conjugate acid proton exchange polymer in which the acidic aromatic unit is ionically bonded to a non-coordinating counter-anion A-. An ion exchange step is then performed combining the intermediate conjugate acid proton exchange polymer with a metal tetrafluoroborate compound with the general formula MBF4, wherein BF4 is a tetrafluoroborate ion (BF4-) and M is a sodium ion (Na+), a potassium ion (K+), a cesium ion (Cs+), ammonium (NH4+) or tetraalkylammonium (R4N+) wherein each R is independently hydrogen or a wholly or partially substituted or unsubstituted alkyl group with one to twenty, one to ten, one to eight, one to six or one to four carbon atoms, such as, for example, a methyl, ethyl, propyl or butyl group.Metal M combines with the counter-anion A- to form a salt of general formula MA, and the tetrafluoroborate ion (BF4-) replaces A- as the counter-anion bonded to the acidic aromatic unit. The ion exchange step therefore results in a conjugated acid proton exchange polymer ionically bonded to a non-coordination tetrafluoroborate counter-anion.

[0089] In some examples, the exchange polymer Petition 870250102744, dated 10 / 11 / 2025, page 48 / 84 41 / 70 Conjugated acid proton exchange polymers are electrically conductive, in addition to being proton-conductive. In these examples, the conjugated acid proton exchange polymer is produced from an electrically conductive polymer, such as a polyaniline or a polypyrrole polymer. In other examples, the conjugated acid proton exchange polymer is electrically non-conductive. In these examples, the conjugated acid proton exchange polymer is produced from an electrically non-conductive polymer.

[0090] The conversion of weakly basic polymers into proton-conducting conjugate acid polymers will now be described with reference to weakly basic PBI polymers, but the principles described here can be applied to any other basic aromatic polymers.

[0091] PBI polymers are a class of polymers composed of PBI polymer molecules. PBI polymer molecules have a repeating unit that includes a benzimidazole unit as at least part of a back chain. The benzimidazole unit comprises a benzimidazole moiety or a derivative thereof. Benzimidazole is a heterocyclic aromatic organic compound with a phenyl group and an imidazole group that share two carbon atoms in their ring structures. The overall structure of benzimidazole is shown in the following formula (I): Petition 870250102744, dated 10 / 11 / 2025, page 49 / 84 42 / 70 (I)

[0092] An example of a PBI polymer with one benzimidazole unit per repeating unit in a main chain is poly(2,5-benzimidazole) (AB-PBI), shown below as Formula (II), and examples of PBI polymers with two benzimidazole units per repeating unit in a main chain are poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (m-PBI), shown below as Formula (III), and 4F-PBI (a fluorinated derivative of m-PBI), shown below as Formula (IV). (II): AB-PBI (III): m-PBI (IV): 4F-PBI Petition 870250102744, dated 10 / 11 / 2025, page 50 / 84 43 / 70

[0093] Other examples of PBI polymers include, but are not limited to, poly{2,6-(2,6-naphthylidene)-1,7dihydrobenzo[1,2-d;4,5-d]diimidazole}; poly 2,2'-(2,6naphthylidene)-5,5'-bibenzimidazole; poly-2,2'-(2,6-pyridine)5,5'-bibenzimidazole; poly-2,2'-(2,5-pyridine) 5,5'bibenzimidazole; poly-2,2'-(2,2,-bipyridine-5,5,)-5,5'bibenzimidazole); poly-2,2'-(3,5-pyrazole)-5,5bibenzimidazole; poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole; poly-2,2'-(pyridylene-3,5)-5,5'-bibenzimidazole; poly2,2'-(furylene-2,5)-5,5'-bibenzimidazole; poly-2.2(naphthalene-1,6)-5,5'-bibenzimidazole; poly-2,2'(biphenylene-4,4)-5,5'-bibenzimidazole; poly-2,2'- amylene5,5'-bibenzimidazole; poly-2,2'- octamethylene-5,5'bibenzimidazole; poly-2,6-(m-phenylene)-diimidazolebenzene; poly-2,2'- cyclohexenyl-5,5'-bibenzimidazole; poly-2,2'-(mphenylene)-5.5'di(benzimidazole)ether; poly-2,2'-(m-phenylene)5,5-di(benzimidazole)sulfone; poly-2,2'-(m-phenylene)-5,5di(benzimidazole)sulfone; poly-2,2'-(m-phenylene)-5,5di(benzimidazole)methano; poly-2-2-(m-phenylene)-5.5(di(benzimidazole)propane 2,2; poly-2,2-(m-phenylene)-5'5di(benzimidazole)ethylene-1,2; and derivatives of any of the foregoing (including substituted (e.g., fluorinated) and / or branched derivatives).

[0094] In some examples, a PBI polymer is a. Petition 870250102744, dated 10 / 11 / 2025, page 51 / 84 44 / 70 copolymer comprising one or more additional repeating units, which may or may not include a benzimidazole unit in a main chain, in a side chain, or in both.

[0095] PBI polymers, which are weakly basic, can be converted into robust acidic polymers through treatments with strong acids in simple acid-base conjugation reactions. The resulting polybenzimidazolium polymers (hereinafter referred to as “PBI+ polymers”) have acidic aromatic units that are conjugate acids of the weakly basic aromatic units of the original PBI polymers. PBI+ polymers are ionic and strongly acidic and therefore have high conductivity for cations. Under the aqueous conditions of water electrolysis and hydrogen fuel cells, the polybenzimidazolium unit readily dissociates to form an equilibrium mixture of neutral PBI and a hydrated proton (HsO+). Thus, readily dissociable polybenzimidazolium units can serve as proton transport agents. As a result, PBI+ polymers can be used in ionomer and proton exchange membrane (PEM) applications.PBI+ acid polymers are simple and advanced alternatives to current versions of a polymer doped with poly(phosphoric acid) (PPA) (e.g., PBI-PPA).

[0096] In a PBI polymer molecule, an amine Petition 870250102744, dated 10 / 11 / 2025, page 52 / 84 45 / 70 A tertiary benzimidazole unit (e.g., N of the N=C group) reacts with a strong acid via an acid-base reaction to produce a benzimidazolium unit (a conjugate acid of the weakly basic benzimidazole unit) and a counter-anion (a conjugate base of the strong acid) ionically bonded to the benzimidazolium unit.

[0097] The molecular structures of PBI+ polymers suggest that non-coordinating counter-anions do not have a direct role in electrochemical processes because the main function of counter-anions is to neutralize cationic charges in the PBI+ polymer structures. As a result, non-coordinating counter-anions do not participate, directly or indirectly, in electrochemical processes and do not inhibit the catalyst cycle by binding to metal catalysts.

[0098] In some examples, the counter-anion comprises tetrafluoroborate ([BF4-]), a non-coordinating ion containing tetravalent boron that remains stable and passive during electrochemical processes. Other suitable counter-anions may include, for example, hexafluorophosphate ([PFe-]), hexafluoroantimonate ([SbFe-]), BF2, AlF3, fluorinated bismuth, fluorinated antimony, fluorinated phosphorus, fluorinated tin, fluorinated zirconium and / or fluorinated titanium.

[0099] The PBI+ polymers described here are all intrinsically ionic, resembling ionic liquids. Petition 870250102744, dated 10 / 11 / 2025, page 53 / 84 46 / 70 which are known to accelerate / facilitate electrochemical reactions. Illustrative proton-conducting PBI+ polymers and methods for manufacturing proton-conducting PBI+ polymers will now be described.

[00100] FIG. 1 shows an illustrative reaction scheme for producing a proton-conducting PBI+ polymer ionically bonded to a tetrafluoroborate counter-anion. As shown in FIG. 1, an m-PBI polymer is combined with tetrafluoroboric acid (HBF4). Tetrafluoroboric acid is a very strong acid and reacts with the tertiary nitrogen of a benzimidazole unit in an acid-base reaction. The reaction produces a benzimidazolium unit and a tetrafluoroborate counter-anion (BF4-) ionically bonded to the benzimidazolium unit. The benzimidazolium unit is a strong conjugate acid of the weakly basic aromatic benzimidazole unit. The tetrafluoroborate counter-anion is the conjugate base of tetrafluoroboric acid.The tetrafluoroborate counter-anion contains a tetravalent anionic boron atom and is therefore neither coordinated nor oxidizing, which makes the tetrafluoroborate counter-anion highly stable under the adverse electrochemical conditions of electrochemical cell applications such as water electrolysis and fuel cells. The tetrafluoroborate counter-anion is also incapable of poisoning the catalyst due to its lack of... Petition 870250102744, dated 10 / 11 / 2025, pp. 54 / 84 47 / 70 connection with metal catalysts.

[00101] In the example in FIG. 1, only one benzimidazole unit is converted into one benzimidazole unit in each repeating unit. In other examples, both benzimidazole units of each repeating unit are converted into one benzimidazole unit. In other examples, the degree of proton charge can be controlled as desired by controlling the molar ratio of HBF4 to benzimidazole units.

[00102] FIG. 2 shows another illustrative reaction scheme for the production of a PBI+ polymer ionically linked to a tetrafluoroborate counter-anion. In a first step, m-PBI is combined with hydrofluoric acid (HF). Hydrofluoric acid is a very strong acid and reacts with the tertiary nitrogen of a benzimidazole unit in an acid-base reaction. The first step produces an intermediate PBI+ polymer with a benzimidazole unit ionically linked to a fluorine counter-anion. In a second step (a fluorine treatment step), the intermediate PBI+ polymer is combined with boron trifluoride (e.g., in the form of BF3 etherate (Et2O)). Boron trifluoride combines with the fluoride counter-anion to form a tetrafluoroborate counter-anion, resulting in a PBI+ polymer that includes a benzimidazolium unit ionically linked to a tetrafluoroborate counter-anion. Petition 870250102744, dated 10 / 11 / 2025, page 55 / 84 48 / 70

[00103] FIG. 3 shows an illustrative reaction scheme for the production of a PBI+ polymer ionically linked to any of several different counter-anions. In a first step, m-PBI is combined with hydrofluoric acid (HF). Hydrofluoric acid is a very strong acid and reacts with the tertiary nitrogen of a benzimidazole unit in an acid-base reaction. The first step produces an intermediate PBI+ polymer with a benzimidazole unit ionically linked to a fluorine counter-anion. In a second step (a fluorine treatment step), the intermediate PBI+ polymer is combined with a metallic fluoride with the general formula MFn, where M is beryllium (Be), aluminum (Al), bismuth (Bi), antimony (Sb), phosphorus (P), tin (Sn), zirconium (Zr) or titanium (Ti) and n corresponds to a valence of M.Metal fluoride combines with the fluoride counter-anion to form a counter-anion with the general formula [MF(n+i)]_e, thus producing a strongly acidic PBI+ polymer ionically linked to a counter-anion.

[00104] FIG. 4 shows another illustrative reaction scheme for producing a PBI+ polymer ionically linked to a tetrafluoroborate counter-anion. In a first step, m-PBI is combined with an acid with the general formula HA, where A is fluorine (F), chlorine (Cl), bromine (Br), HSO4, SO4, H2PO4, HPO4, PO4, or any type of polyphosphate ion. Petition 870250102744, dated 10 / 11 / 2025, pp. 56 / 84 49 / 70 derived from any type of polyphosphoric acid. Suitable examples of polyphosphoric acids include, among others, diphosphoric acid, triphosphoric acid, tetraphosphoric acid, and trimetaphosphoric acid. The acid HA reacts with the tertiary nitrogen of a benzimidazole unit in an acid-base reaction. The first step produces a PBI+ polymer intermediate with a benzimidazolium unit ionically linked to an A- counter-anion. In a second step (an ion-exchange step), the A- counter-anion is exchanged for a tetrafluoroborate counter-anion ([BF4-]), which is a non-coordinating counter-anion.The second step is carried out by combining the intermediate polymer PBI+ with a metallic tetrafluoroborate compound with the general formula mbf4, wherein BF4 is a tetrafluoroborate ion (BF4-) and M is a sodium ion (Na+), a potassium ion (K+), a cesium ion (Cs+), ammonium (NH4+) or tetraalkylammonium (R4N+) wherein each R is independently hydrogen or a fully or partially substituted or unsubstituted alkyl group, which may have from one to twenty, one to ten, one to eight, one to six or one to four carbon atoms, such as, for example, a methyl, ethyl, propyl or butyl group. The metallic tetrafluoroborate compound combines with the fluoride counter-anion to form a tetrafluoroborate counter-anion, resulting in a strongly acidic PBI+ polymer, ionically linked to a non-coordinating tetrafluoroborate counter-anion. Petition 870250102744, dated 10 / 11 / 2025, p. 57 / 84 50 / 70

[00105] The examples and reaction schemes described above can be extended to other applications, including the cross-linking of fluoroboric acid-functionalized polymers with basic aromatic polymers to form a conjugated acid proton exchange polymer. In some examples, the fluoroboric acid-functionalized polymer is a fluoroboric acid-functionalized sulfonic acid polymer, which includes sulfonic acid-functionalized polymers (e.g., Nation™ and Aquivion® polymers) in which one or more pendant sulfonic acid groups have reacted with bf3, resulting in the following structure with a pendant fluoroboric acid group (-bf3h) (e.g., in one or more side chains or side groups): >0 FH® >ii l© 4-SOB—F ? OF

[00106] Polymers functionalized with fluoroboric acid are combined with a basic aromatic polymer, such as PBI, PANI, or any other basic aromatic polymer described in this document. The pendant fluoroboric acid groups react with the basic aromatic units of the basic aromatic polymer in an acid-base reaction, similar to the acid-base reaction in FIG. 1, to crosslink the fluoroboric acid-functionalized polymer with the basic aromatic polymer. One molecule Petition 870250102744, dated 10 / 11 / 2025, pp. 58 / 84 51 / 70 of crosslinked conjugate acid proton exchange polymer includes a first polymer molecule comprising an acidic aromatic unit, wherein the acidic aromatic unit is a conjugate acid of a basic aromatic unit; and a second polymer molecule comprising a trifluoroborate group, wherein the trifluoroborate group is a conjugate base of a fluoroboric acid group.

[00107] The first polymer molecule and the second polymer molecule are cross-linked by an ionic bond between the acidic aromatic unit and the trifluoroborate group. Examples of crosslinked conjugated acid proton exchange polymers include, without limitation, PBI+-PFSA (polyfluorosulfonic acid) polymers (e.g., PBI+Nafion™ polymers and PBI+-Aquivion® polymers), PBI+-SPSF (sulfonated polysulfone) polymers, PBI+-SPEEK (sulfonated poly(ether ketone)) polymers, PANI-PFSA polymers (e.g., PANI-Nafion™ polymers and PANI-Aquivion® polymers), PANI-SPSF polymers, PANI-SPEEK polymers, PPy-PFSA polymers (e.g., PPy-Nafion™ polymers and PPy-Aquivion® polymers), PPy-SPSF polymers, and PPy-SPEEK polymers. In some examples, more than two polymers can be cross-linked, such as three or four polymers.

[00108] It should be recognized that other polymers functionalized with fluoroboric acid can be crosslinked. Petition 870250102744, dated 10 / 11 / 2025, page 59 / 84 52 / 70 with a basic aromatic polymer, in addition to fluoroboric acid-functionalized sulfonic acid polymers. Fluoroboric acid-functionalized polymers include any polymers with fluoroboric acid pendant groups, such as, without limitation, any fluoroboric acid-functionalized polymers described in International Patent Application No. PCT / US2024 / 015409, filed February 12, 2024, which is incorporated herein by reference in its entirety. Cross-linking a fluoroboric acid-functionalized polymer with a basic aromatic polymer in this way increases the dimensional tolerance of the cross-linked conjugated acid proton exchange polymer.

[00109] FIG. 5 shows an illustrative proton exchange membrane water electrolysis system 500 (PEM 500 water electrolysis system) incorporating PEMs and / or conjugated acid proton exchange polymer ionomers (e.g., PBI+ polymer PEMs and / or ionomers). The PEM 500 water electrolysis system uses electricity to split water into oxygen (O2) and hydrogen (H2) via an electrochemical reaction. The configuration of the PEM 500 water electrolysis system is merely illustrative and not limiting, as other suitable configurations, as well as other suitable water electrolysis systems, may incorporate conjugated acid proton exchange polymers. Petition 870250102744, dated 10 / 11 / 2025, pp. 60 / 84 53 / 70

[00110] As shown in FIG. 5, the PEM 500 water electrolysis system includes a membrane electrode assembly 502 (MEA 502), porous transport layers 504-1 and 504-2 (e.g., gas diffusion layers), bipolar plates 506-1 and 506-2, and an electrical power supply 508. The PEM 500 water electrolysis system may also include additional or alternative components not shown in FIG. 5 as needed for a specific implementation.

[00111] The MEA 502 includes a PEM 510 positioned between a first catalyst layer 512-1 and a second catalyst layer 512-2. The PEM 510 electrically isolates the first catalyst layer 512-1 from the second catalyst layer 512-2 and, at the same time, provides selective conductivity of cations such as protons (H+) and is impermeable to gases such as hydrogen and oxygen. The PEM 510 can be implemented by a conjugated acid proton exchange polymer (e.g., a PBI+ polymer), as described in this document, or by any other suitable polymer.

[00112] The first layer of catalyst 512-1 and the second layer of catalyst 512-2 are electrically conductive electrodes that include solid catalyst supports bonded to electrocatalyst particles (not shown), such as platinum group metals, metal alloys, and / or metal oxides. The first layer of catalyst 512 Petition 870250102744, dated 10 / 11 / 2025, pp. 61 / 84 54 / 70 and the second layer of catalyst 512-2 may also include one or more ionomers mixed with the solid catalyst supports and electrochemical catalyst particles. The ionomers may be implemented by a conjugated acid proton exchange polymer (e.g., a PBI+ polymer), as described in this document, or by any other suitable ionomer. In some examples, the ionomers are implemented by an electrically conductive conjugated acid proton exchange polymer (e.g., a conjugated acid proton exchange polyaniline polymer).

[00113] MEA 502 is placed between porous transport layers 504-1 and 504-2, which, in turn, are placed between bipolar plates 506-1 and 506-2 with flow channels 514-1 and 514-2 located between bipolar plates 506 and porous transport layers 504.

[00114] In MEA 502, the first catalyst layer 512-1 functions as an anode and the second catalyst layer 512-2 functions as a cathode. When the PEM 500 water electrolysis system is powered by the power supply 508, an oxygen evolution reaction (OER) occurs in the first layer / anode of catalyst 512-1, facilitated by the electrocatalysts attached to the solid catalyst supports in the first layer / anode of catalyst 512-1. The OER is represented by the following half Petition 870250102744, dated 10 / 11 / 2025, pp. 62 / 84 55 / 70 electrochemical reaction: H₂O → O₂ + 4 H⁺ + 4 e⁻

[00115] Protons are conducted from the first catalyst / anode layer 512-1 to the second catalyst / cathode layer 512-2 via the PEM 510, and electrons are conducted from the first catalyst / anode layer 512-1 to the second catalyst / cathode layer 512-2 via the conductive path around the PEM 510. The PEM 510 allows the transport of protons (H+) and water from the first catalyst / anode layer 512-1 to the second catalyst / cathode layer 512-2, but is impermeable to oxygen and hydrogen. In the second catalyst / cathode layer 512-2, protons combine with electrons in a hydrogen evolution reaction (HER), facilitated by electrocatalysts attached to the solid catalyst supports in the second catalyst / anode layer 512-2. The HER is represented by the following electrochemical half-reaction: 4H++ 4e-->2Hz

[00116] The OER and HER are two complementary electrochemical reactions for the splitting of water by electrolysis, represented by the following general water electrolysis reaction: H2O 2 H2+ O2

[00117] FIG. 6 shows a fuel cell of Petition 870250102744, dated 10 / 11 / 2025, pp. 63 / 84 56 / 70 Illustrative Proton Exchange Membrane 600 (PEM 600 Fuel Cell) which includes PEMs and / or conjugated acid proton exchange polymer ionomers (e.g., PBI+ polymer PEMs and / or ionomers). The PEM 600 fuel cell produces electricity as a result of electrochemical reactions. In this example, the electrochemical reactions involve the reaction of hydrogen gas (H2) and oxygen gas (O2) to produce water and electricity. The PEM 600 fuel cell configuration is merely illustrative and not limiting.

[00118] As shown in FIG. 6, the PEM 600 fuel cell includes a membrane electrode assembly 602 (MEA 602), porous transport layers 604-1 and 604-2 (e.g., gas diffusion layers), bipolar plates 606-1 and 606-2. An electrical load 608 can be electrically connected to the MEA 602 and driven by the PEM 600 fuel cell. The PEM 600 fuel cell may also include additional or alternative components not shown in FIG. 6 as needed for a specific implementation.

[00119] MEA 602 includes a PEM 610 positioned between a first catalyst layer 612-1 and a second catalyst layer 612-2. The PEM 610 electrically isolates the first catalyst layer 612-1 from the second catalyst layer 612-2 and, at the same time, provides Petition 870250102744, dated 10 / 11 / 2025, pages 64 / 84 57 / 70 selective conductivity of cations, such as protons (H+), and is impermeable to gases such as hydrogen and oxygen. PEM 610 can be implemented by any suitable PEM described in this document, including any conjugated acid proton exchange polymer described or contemplated in this document.

[00120] The first catalyst layer 612-1 and the second catalyst layer 612-2 are electrically conductive electrodes that include solid catalyst supports that bind electrocatalyst particles (not shown), such as platinum metals, metal alloys, and / or metal oxides. The first catalyst layer 612-1 and the second catalyst layer 612-2 may also include one or more ionomers mixed with the solid catalyst supports and the electrochemical catalyst particles. The ionomers may be implemented by any suitable polymers or ionomers described herein, including any conjugated acid proton exchange polymers described herein, or by any other suitable ionomers. In some examples, the ionomers are implemented by an electrically conductive conjugated acid proton exchange polymer (e.g., a conjugated acid proton exchange polyaniline polymer).

[00121] MEA 602 is placed between the porous transport layers 604-1 and 604-2, which, in turn, are Petition 870250102744, dated 10 / 11 / 2025, pages 65 / 84 58 / 70 placed between bipolar plates 606-1 and 606-2, with flow channels 614 located between them. In MEA 602, the first catalyst layer 612-1 functions as a cathode and the second catalyst layer 612-2 functions as an anode. The first catalyst / cathode layer 612-1 and the anode 612-2 are electrically connected to the load 608, and the electricity generated by the PEM fuel cell 600 drives the load 608.

[00122] During the operation of the PEM 600 fuel cell, hydrogen gas (H2) flows to the anode side of the PEM 600 fuel cell and oxygen gas (O2) flows to the cathode side of the PEM 600 fuel cell. In the second layer / anode of catalyst 612-2, hydrogen molecules are catalytically split into protons (H+) and electrons (e-) according to the following hydrogen oxidation reaction (HOR), which is facilitated by electrocatalyst particles attached to the solid catalyst supports in the second layer / anode of catalyst 612-2: H24 H* + 4 e

[00123] Protons are conducted from anode 612-2 to the first catalyst / cathode layer 612-1 via PEM 600, and electrons are conducted from the second catalyst / anode layer 612-2 to the first catalyst / cathode layer 612-1 around PEM 610 via a conductive path and charge 608. In the first layer of Petition 870250102744, dated 10 / 11 / 2025, pp. 66 / 84 59 / 70 catalyst / cathode 612-1, protons and electrons combine with oxygen gas according to the following oxygen reduction reaction (ORR), which is facilitated by electrochemical catalyst particles attached to the solid catalyst supports in the first layer of catalyst / anode 612-1:

[00124] Thus, the overall electrochemical reaction of the PEM 600 fuel cell is: H2 + O2 — 2 H2O

[00125] In the overall reaction, the PEM 600 fuel cell produces water in the first catalyst / cathode layer 6121. Water can flow from the first catalyst / cathode layer 612-1 to the second catalyst / anode layer 612-2 via the PEM 610 and can be removed via outlets on the cathode and / or anode side of the PEM 600 fuel cell. The overall reaction generates electrons at the anode that drive the load 608.

[00126] In the examples of FIGS. 14 and 5, MEA 502 and MEA 602 include 512 / 412 catalyst layers formed on PEM 510 / 410. In alternative configurations, the 512 / 412 catalyst layers can be coated onto PEM 110 / 410 to form a catalyst-coated membrane (CCM). For example, the 512 / 212 catalyst layers can be formed in a single process or in stages and sprayed onto the PEM. Petition 870250102744, dated 10 / 11 / 2025, pp. 67 / 84 60 / 70 510 / 410.

[00127] Conjugated acid proton exchange polymers have been described in this document for use in electrochemical cell applications, such as water electrolysis and hydrogen fuel cell applications. However, conjugated acid proton exchange polymers can also be used in other applications. For example, the pKa of conjugated acid proton exchange polymers can be controlled to a desired level for many applications, including electrochemical processes for ammonia production. For example, the pKa of conjugated acid proton exchange polymers can be controlled to be higher than the pKa of conventional PEMs currently used in ammonia synthesis processes.

[00128] Several examples and embodiments have been described and illustrated in this document. However, it is evident that various modifications and alterations may be made, and other embodiments may be implemented, without departing from the scope of the following claims. For example, certain features of an embodiment described in this document may be combined with or replaced by features of another embodiment described in this document. The description and drawings should therefore be considered in an illustrative and not restrictive sense.

[00129] The advantages and features of the present Petition 870250102744, dated 10 / 11 / 2025, pp. 68 / 84 61 / 70 description can be further detailed in the following examples:

[00130] Example 1. A conjugate acid proton exchange polymer molecule comprising: an acidic aromatic unit in a main chain or in a side chain, wherein the acidic aromatic unit is a conjugate acid of a basic aromatic unit; and a non-coordinating counter-anion ionically linked to the acidic aromatic unit.

[00131] Example 2. The conjugate acid proton exchange polymer molecule of example 1, wherein the non-coordinating counteranion is a conjugate base of a strong acid.

[00132] Example 3. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises tetrafluoroborate.

[00133] Example 4. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises hexafluorophosphate.

[00134] Example 5. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises hexafluoroantimonate.

[00135] Example 6. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises benzenesulfonatotrifluoroborate (PhSOs(BF3)-). Petition 870250102744, dated 10 / 11 / 2025, pp. 69 / 84 62 / 70

[00136] Example 7. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises sulfate-di(trifluoroborate) (SO4 (BF3) 22-).

[00137] Example 8. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises beryllium fluoride, aluminum fluoride, fluorinated bismuth, fluorinated antimony, fluorinated phosphorus, fluorinated tin, fluorinated zirconium, or fluorinated titanium.

[00138] Example 9. The conjugate acid proton exchange polymer molecule of Example 1, wherein the non-coordinating counteranion comprises a metal fluoroborate with the general formula [MF(n+i)]—wherein M is beryllium (Be), aluminum (Al), bismuth (Bi), antimony (Sb), phosphorus (P), tin (Sn), zirconium (Zr), or titanium (Ti) and ε corresponds to the valence of M.

[0132] Example 10. The conjugate acid proton exchange polymer molecule of Example 1, wherein the basic aromatic unit comprises aniline or an aniline derivative.

[00139] Example 11. The conjugate acid proton exchange polymer molecule of Example 1, wherein the basic aromatic unit comprises an imidazole group or a benzimidazole group.

[00140] Example 12. The exchange polymer molecule Petition 870250102744, dated 10 / 11 / 2025, pp. 70 / 84 63 / 70 conjugate acid proton exchange polymer molecule from example 1, where the conjugate acid proton exchange polymer molecule is electrically conductive.

[00141] Example 13. A method for manufacturing a conjugate acid proton exchange polymer molecule, comprising: protonation of a basic aromatic unit of a basic aromatic polymer molecule to form an acidic aromatic unit, wherein the acidic aromatic unit is a conjugate acid of the basic aromatic unit; and ionic bonding of a non-coordinating counter-anion to the acidic aromatic unit.

[00142] Example 14. The method of example 13, wherein the protonation of the basic aromatic unit and the ionic bonding of the non-coordinating counter-anion with the acidic aromatic unit comprise the reaction of the basic aromatic unit with an acid in an acid-base reaction, wherein a conjugate base of the acid comprises the non-coordinating counter-anion.

[00143] Example 15. The method of example 14, wherein the acid comprises fluoroboric acid.

[00144] Example 16. The method of example 14, wherein the acid comprises hexafluorophosphoric acid.

[00145] Example 17. The method of example 14, wherein the acid comprises fluoroantimonic acid.

[00146] Example 18. The method of example 14, wherein the acid comprises a sulfuric acid-trifluoride complex. Petition 870250102744, dated 10 / 11 / 2025, pp. 71 / 84 64 / 70 boron with the general structure:

[00147] Example 19. The method of example 14, wherein the acid comprises a complex of boron trifluoride and benzenesulfonic acid with the general structure:

[00148] Example 20. The method of example 14, wherein the acid comprises a benzene disulfonic acid boron trifluoride complex with the general structure: ah® F , OFH® \\ ।1Ia O'X' OF .

[00149] Example 21. The method of example 14, wherein the acid comprises phenyltrifluoroboric acid with the general structure: or phenyl 1,4-di(trifluoro)boric acid with the general structure: Petition 870250102744, dated 10 / 11 / 2025, pp. 72 / 84 65 / 70

[00150] Example 22. The method of example 14, wherein the acid comprises a complex of boron trifluoride and phosphoric acid with the general structure:

[00151] Example 23. The method of example 13, wherein: the protonation of the basic aromatic unit comprises the reaction of the basic aromatic unit with hydrofluoric acid in an acid-base reaction, wherein a conjugate base of hydrofluoric acid comprises a fluorine counter-anion ionically bonded to the acidic aromatic unit; and the ionically bonding of the non-coordinating counter-anion to the acidic aromatic unit comprises the reaction of the fluorine counter-anion with boron trifluoride.

[00152] Example 24. The method of example 13, wherein: the protonation of the basic aromatic unit comprises the reaction of the basic aromatic unit with hydrofluoric acid in an acid-base reaction, wherein a conjugate base of hydrofluoric acid comprises a fluoride counter-anion ionically bonded to the acidic aromatic unit; and the ionic bond Petition 870250102744, dated 10 / 11 / 2025, pp. 73 / 84 66 / 70 of the non-coordinating counter-anion with the acidic aromatic unit comprises the reaction of the fluoride counter-anion with a metallic fluoride with the general formula MFn, where M is beryllium (Be), aluminum (Al), bismuth (Bi), antimony (Sb), phosphorus (P), tin (Sn), zirconium (Zr) or titanium (Ti) and n corresponds to the valence of M.

[00153] Example 25. The method of example 13, wherein: the protonation of the basic aromatic unit comprises the reaction of the basic aromatic unit with an acid in an acid-base reaction, wherein a conjugate base of the acid comprises a coordinating counter-anion ionically bonded to the acidic aromatic unit; and the ionically bonding of the non-coordinating counter-anion to the acidic aromatic unit comprises carrying out an ion-exchange reaction to exchange the coordinating counter-anion for the non-coordinating counter-anion.

[00154] Example 26. The method of example 25, wherein the acid has the general formula HA, wherein A is F, Cl, Br, HSO4, SO4, H2PO4, HPO4, PO4, or a polyphosphate ion.

[00155] Example 27. The method of example 25, wherein the ion exchange reaction comprises the reaction of a metal tetrafluoroborate compound with the general formula MBF4, wherein M is a sodium ion (Na+), a potassium ion (K+), a cesium ion (Cs+), ammonium (NH4+) or tetraalkylammonium with the general formula R4N+, wherein each R is independently hydrogen or a wholly or partially alkyl group. Petition 870250102744, dated 10 / 11 / 2025, pp. 74 / 84 67 / 70 replaced or not replaced.

[00156] Example 28. The method of example 13, wherein the basic aromatic polymer molecule comprises a polyaniline polymer.

[00157] Example 29. The method of example 13, wherein the basic aromatic polymer molecule comprises a polybenzimidazole polymer.

[00158] Example 30. The method of example 13, in which the basic aromatic polymer molecule is electrically conductive.

[00159] Example 31. A membrane electrode assembly comprising: a first catalyst layer; a second catalyst layer; and a proton exchange membrane positioned between the first catalyst layer and the second catalyst layer; wherein at least one of the layers of the first catalyst, the second catalyst and the proton exchange membrane is formed from a conjugate acid proton exchange polymer comprising: acidic aromatic units in a main chain or in a side chain, wherein the acidic aromatic units are a conjugate acid of a basic aromatic unit; and non-coordinating counter-anions ionically linked to the acidic aromatic units.

[00160] Example 32. The membrane electrode assembly of example 31, in which: the proton exchange polymer of acid Petition 870250102744, dated 10 / 11 / 2025, pages 75 / 84 68 / 70 conjugate is electrically conductive; and at least one of the layers of the first or second catalyst is formed by the conjugate acid proton exchange polymer.

[00161] Example 33. The membrane electrode assembly of example 32, wherein the proton exchange membrane is formed by an additional conjugated acid proton exchange polymer that is electrically non-conductive.

[00162] Example 34. The membrane electrode assembly of example 31, wherein the conjugated acid proton exchange polymer comprises a polybenzimidazolium polymer.

[00163] Example 35. The membrane electrode assembly of example 31, wherein the conjugated acid proton exchange polymer comprises a polyaniline polymer.

[00164] Example 36. A method for manufacturing a conjugated acid proton exchange polymer, the method comprises: crosslinking a fluoroboric acid functionalized polymer molecule with a basic aromatic polymer molecule.

[00165] Example 37. The method of example 36, wherein the fluoroboric acid functionalized polymer molecule comprises a polyfluorosulfonic acid polymer molecule with one or more sulfonic acid groups functionalized with a fluoroboric acid group.

[00166] Example 38. The method of example 36, in which the basic aromatic polymer molecule comprises a Petition 870250102744, dated 10 / 11 / 2025, pp. 76 / 84 69 / 70 polybenzimidazole (PBI) polymer molecule.

[00167] Example 39. The method of example 36, wherein the basic aromatic polymer molecule comprises a polyaniline polymer (PANI) molecule.

[00168] Example 40. The method of example 36, in which the cross-linking of the fluoroboric acid-functionalized polymer molecule with the basic aromatic polymer molecule comprises: the reaction of a fluoroboric acid group of the fluoroboric acid-functionalized polymer molecule with a basic aromatic unit of the basic aromatic polymer molecule in an acid-base reaction.

[00169] Example 41. A conjugate acid proton exchange polymer comprising: a first polymer molecule comprising an acidic aromatic unit, wherein the acidic aromatic unit is a conjugate acid of a basic aromatic unit; and a second polymer molecule comprising a trifluoroborate group, wherein the trifluoroborate group is a conjugate base of a fluoroboric acid group; in which the first polymer molecule and the second polymer molecule are cross-linked by an ionic bond between the acidic aromatic unit and the trifluoroborate group.

[00170] Example 42. The conjugated acid proton exchange polymer of Example 40, wherein the first polymer molecule comprises a polybenzimidazole (PBI) polymer. Petition 870250102744, dated 10 / 11 / 2025, pp. 77 / 84 70 / 70

[00171] Example 43. The conjugated acid proton exchange polymer of example 40, wherein the first polymer molecule comprises a polyaniline polymer (PANI).

[00172] Example 44. The conjugated acid proton exchange polymer of Example 40, wherein the second polymer molecule comprises a sulfonic acid polymer functionalized with fluoroboric acid. Petition 870250102744, dated 10 / 11 / 2025, pp. 78 / 84

Claims

1 / 11 CLAIMS 1. Conjugate acid proton exchange polymer molecule, characterized in that it comprises: an acidic aromatic unit in a main chain or in a side chain, wherein the acidic aromatic unit is a conjugate acid of a basic aromatic unit; and an uncoordinated counter-anion ionically linked to the acidic aromatic unit.

2. Conjugate acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion is a conjugate base of a strong acid.

3. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion comprises tetrafluoroborate.

4. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion comprises hexafluorophosphate.

5. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion comprises hexafluoroantimonate.

6. Conjugated acid proton exchange polymer molecule, according to claim 1, characterized in that the non-coordinating counter-anion comprises benzenesulfonate-trifluoroborate (PhSOs (BF3)-).

7. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion comprises sulfate-di(trifluoroborate) (SO4 (BF3) 22-).

8. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion comprises beryllium fluoride, aluminum fluoride, fluorinated bismuth, fluorinated antimony, fluorinated phosphorus, fluorinated tin, fluorinated zirconium or fluorinated titanium.

9. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the non-coordinating counter-anion comprises a metal fluoroborate with the general formula [MF(n+i)]- wherein M is beryllium (Be), aluminum (Al), bismuth (Bi), antimony (Sb), phosphorus (P), tin (Sn), zirconium (Zr) or titanium (Ti) and n corresponds to the valence of M.

10. Conjugate acid proton exchange polymer molecule according to claim 1, characterized in that the basic aromatic unit comprises aniline or an aniline derivative.

11. Conjugated acid proton exchange polymer molecule, according to claim 1, characterized in that the basic aromatic unit comprises an imidazole group or a benzimidazole group. Petition 870250091180, dated 06 / 10 / 2025, page 29 / 39 3 / 11 12. Conjugated acid proton exchange polymer molecule according to claim 1, characterized in that the conjugated acid proton exchange polymer molecule is electrically conductive.

13. A method for manufacturing a conjugated acid proton exchange polymer molecule, characterized in that it comprises protonating a basic aromatic unit of a basic aromatic polymer molecule to form an acidic aromatic unit, wherein the acidic aromatic unit is a conjugate acid of the basic aromatic unit; and ionically linking a non-coordinating counter-anion to the acidic aromatic unit.

14. A method according to claim 13, characterized in that protonating the basic aromatic unit and ionically linking the non-coordinating counter-anion with the acidic aromatic unit comprises reacting the basic aromatic unit with an acid in an acid-base reaction, wherein a conjugate base of the acid comprises the non-coordinating counter-anion.

15. Method according to claim 14, characterized in that the acid comprises fluoroboric acid. Petition 870250091180, dated 06 / 10 / 2025, page 30 / 39 4 / 11 16. Method according to claim 14, characterized in that the acid comprises hexafluorophosphoric acid.

17. Method according to claim 14, characterized in that the acid comprises fluoroantimonic acid.

18. Method according to claim 14, characterized in that the acid comprises a sulfuric acid-boron trifluoride complex with the general structure: H® FOFH® ιθ ii ιθ FBOSOBF I II IFOF .

19. Method according to claim 14, characterized in that the acid comprises a complex of boron trifluoride and benzenesulfonic acid with the general structure:

20. Method, characterized by the fact that, in accordance with claim 14, the acid comprises a benzene disulfonic acid-boron trifluoride complex with the general structure: Petition 870250091180, dated 06 / 10 / 2025, page 31 / 39 5 / 11 21. Method according to claim 14, characterized in that the acid comprises phenyltrifluoroboric acid with the general structure: or phenyl1,4-di(trifluoro)boric acid with the general structure:

22. Method according to claim 14, characterized in that the acid comprises a complex of boron trifluoride and phosphoric acid with the general structure:

23. Method according to claim 13, characterized in that: the protonation of the basic aromatic unit comprises the reaction of the basic aromatic unit with hydrofluoric acid in an acid-base reaction, wherein a conjugate base of hydrofluoric acid comprises a fluoride counter-anion ionically linked to the acidic aromatic unit; and the ionic linkage of the non-coordinating counter-anion with the acidic aromatic unit comprises the reaction of the fluoride counter-anion with boron trifluoride.

24. Method according to claim 13, characterized in that: the protonation of the basic aromatic unit comprises the reaction of the basic aromatic unit with hydrofluoric acid in an acid-base reaction, wherein a conjugate base of hydrofluoric acid comprises a fluoride counter-anion ionically bonded to the acidic aromatic unit; and the ionic bonding of the non-coordinating counter-anion with the acidic aromatic unit comprises the reaction of the fluoride counter-anion with a metallic fluoride having the general formula MFn, wherein M is beryllium (Be), aluminum (Al), bismuth (Bi), antimony (Sb), phosphorus (P), tin (Sn), zirconium (Zr) or titanium (Ti) and n corresponds to the valence of M.

25. Method according to claim 13, characterized in that: the protonation of the basic aromatic unit comprises the reaction of the basic aromatic unit with an acid in an acid-base reaction, wherein a conjugate base of the acid comprises a coordinating counter-anion ionically bonded to the acidic aromatic unit; and the ionic bonding of the non-coordinating counter-anion with the acidic aromatic unit comprises carrying out an ion-exchange reaction to exchange the coordinating counter-anion for the non-coordinating counter-anion.

26. Method according to claim 25, characterized in that the acid has the general formula HA, wherein A is F, Cl, Br, HSO4, SO4, H2PO4, HPO4, PO4 or a polyphosphate anion.

27. Method according to claim 25, characterized in that the ion exchange reaction comprises the reaction of a metal tetrafluoroborate compound with the general formula MBF4, wherein M is a sodium ion (Na+), a potassium ion (K+), a cesium ion (Cs+), ammonium (NH4+) or tetraalkylammonium with the general formula R4N+, wherein each R is independently hydrogen or a wholly or partially substituted or unsubstituted alkyl group.

28. Method according to claim 13, characterized in that the basic aromatic polymer molecule comprises a polyaniline polymer.

29. Method according to claim 13, characterized in that the basic aromatic polymer molecule comprises a polybenzimidazole polymer.

30. Method according to claim 13, characterized in that the basic aromatic polymer molecule is electrically conductive.

31. A membrane electrode assembly, characterized as per Petition 870250091180, dated 06 / 10 / 2025, page 34 / 39 8 / 11, in that it comprises: a first catalyst layer; a second catalyst layer; and a proton exchange membrane positioned between the first catalyst layer and the second catalyst layer; wherein at least one of the layers of the first catalyst, the second catalyst layer, and the proton exchange membrane is formed by a conjugated acid proton exchange polymer comprising: acidic aromatic units in a main chain or in a side chain, wherein the acidic aromatic units are a conjugate acid of a basic aromatic unit; and non-coordinating counter-anions ionically linked to the acidic aromatic units.

32. Membrane electrode assembly according to claim 31, characterized in that: the conjugated acid proton exchange polymer is electrically conductive; and at least one of the layers of the first catalyst or the second catalyst is formed by the conjugated acid proton exchange polymer.

33. Membrane electrode assembly, according to claim 32, characterized in that the proton exchange membrane is formed by an additional conjugated acid proton exchange polymer that is electrically non-conductive. Petition 870250091180, dated 06 / 10 / 2025, page 35 / 39 9 / 11 34. Membrane electrode assembly according to claim 31, characterized in that the conjugated acid proton exchange polymer comprises a polybenzimidazolium polymer.

35. Membrane electrode assembly according to claim 31, characterized in that the conjugated acid proton exchange polymer comprises a polyaniline polymer.

36. Method for manufacturing a conjugated acid proton exchange polymer, the method characterized in that it comprises: the crosslinking of a fluoroboric acid-functionalized polymer molecule with a basic aromatic polymer molecule.

37. Method according to claim 36, characterized in that the fluoroboric acid-functionalized polymer molecule comprises a polyfluorosulfonic acid polymer molecule with one or more sulfonic acid groups functionalized with a fluoroboric acid group.

38. Method according to claim 36, characterized in that the basic aromatic polymer molecule comprises a polybenzimidazole (PBI) polymer molecule. Petition 870250091180, dated 06 / 10 / 2025, pp. 36 / 39 10 / 11 39. Method according to claim 36, characterized in that the basic aromatic polymer molecule comprises a polyaniline polymer (PANI) molecule.

40. A method according to claim 36, characterized in that the cross-linking of the fluoroboric acid-functionalized polymer molecule with the basic aromatic polymer molecule comprises: reacting a fluoroboric acid group of the fluoroboric acid-functionalized polymer molecule with a basic aromatic unit of the basic aromatic polymer molecule in an acid-base reaction.

41. Conjugate acid proton exchange polymer, characterized in that it comprises: a first polymer molecule comprising an acidic aromatic unit, wherein the acidic aromatic unit is a conjugate acid of a basic aromatic unit; and a second polymer molecule comprising a trifluoroborate group, wherein the trifluoroborate group is a conjugate base of a fluoroboric acid group; wherein the first polymer molecule and the second polymer molecule are cross-linked by an ionic bond between the acidic aromatic unit and the trifluoroborate group.

42. Conjugated acid proton exchange polymer, according to claim 40, characterized in that Petition 870250091180, dated 06 / 10 / 2025, page 37 / 39 11 / 11 that the first polymer molecule comprises a polybenzimidazole (PBI) polymer.

43. Conjugated acid proton exchange polymer according to claim 40, characterized in that the first polymer molecule comprises a polyaniline polymer (PANI).

44. Conjugated acid proton exchange polymer according to claim 40, characterized in that the second polymer molecule comprises a sulfonic acid polymer functionalized with fluoroboric acid. Petition 870250091180, dated 06 / 10 / 2025, pp. 38 / 39

Images