WO2012096653A1 - Proton exchange material and method therefor - Google Patents

Proton exchange material and method therefor Download PDF

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Publication number
WO2012096653A1
WO2012096653A1 PCT/US2011/020806 US2011020806W WO2012096653A1 WO 2012096653 A1 WO2012096653 A1 WO 2012096653A1 US 2011020806 W US2011020806 W US 2011020806W WO 2012096653 A1 WO2012096653 A1 WO 2012096653A1
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Prior art keywords
chains
proton exchange
capped
exchange material
recited
Prior art date
Application number
PCT/US2011/020806
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French (fr)
Inventor
Zhiwei Yang
Ned E. Cipollini
Mallika Gummalla
Fuqiang Liu
Joseph S. THRASHER
Richard Edward Fernandez
Todd S. SAYLER
Alfred Waterfeld
Original Assignee
Utc Power Corporation
Toyota Jidosha Kabushiki Kaisha
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Application filed by Utc Power Corporation, Toyota Jidosha Kabushiki Kaisha filed Critical Utc Power Corporation
Priority to JP2013549392A priority Critical patent/JP2014507520A/en
Priority to US13/978,721 priority patent/US20130281555A1/en
Priority to PCT/US2011/020806 priority patent/WO2012096653A1/en
Publication of WO2012096653A1 publication Critical patent/WO2012096653A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This disclosure relates to fluoropolymers that are used as proton exchange materials in applications such as fuel cells.
  • Fuel cells are commonly used for generating electric current.
  • a single fuel cell typically includes an anode catalyst, a cathode catalyst, and an electrolyte between the anode and cathode catalyst for generating an electric current in a known electrochemical reaction between a fuel and an oxidant.
  • the electrolyte may be a fluoropolymer membrane, which is also known as a proton exchange membrane or "PEM.”
  • fluoropolymer membrane is sulfonated tetrafluoroethylene, known as NAFION.
  • Sulfonated tetrafluoroethylene includes proton exchange sites that function to transmit protons between the anode and cathode catalyst.
  • the proton exchange site is at a sulfonic acid group SO 3 H, which terminates a pendent perfluorinated side chain of the polymer.
  • Another common type of fluoropolymer membrane is sulfonamide which also includes proton exchange sites that function to transmit protons between the anode and cathode catalyst.
  • the proton exchange site is at a nitrogen atom - S02-NH-S02-CF3 which terminates a pendent side chain of the polymer.
  • a disclosed proton exchange material includes perfluorinated carbon backbone chains and side chains extending off of the perfluorinated carbon backbone chains.
  • the side chains include cross-link chains that have multiple sulfonimide groups,— S0 2 — NH— S0 2 — .
  • An example method of fabricating a proton exchange material includes forming a polymer having perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains.
  • the perfluorinated side chains include cross-link chains that have multiple sulfonimide groups,— S0 2 — NH— S0 2 — .
  • the disclosed example proton exchange materials may be used for fuel cell proton exchange membranes or other applications where proton exchange is desirable.
  • the disclosed proton exchange material provides the ability to increase the number of proton exchange sites on a molar basis while maintaining resistance to solvents, such as water.
  • solvents such as water.
  • an increase in the number of proton exchange sites in sulfonated tetrafluoroethylene increases proton conductivity but also increases solubility in water, which is detrimental in fuel cell applications.
  • a decrease in the number of proton exchange sites in sulfonated tetrafluoroethylene provides an increase in resistance to water but decreases proton conductivity and debits fuel cell performance.
  • An example proton exchange material includes perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains.
  • the perfluorinated side chains include cross-link chains that have multiple sulfonimide groups,— S0 2 — NH— S0 2 — .
  • the perfluorinated carbon backbone chains have a structure of — (CF 2 )— .
  • the perfluorinated side chains include a general structure of — CxF 2X Oz— , where X is greater than or equal to two and Z is greater than or equal to zero.
  • the side chains have a structure— ⁇ (CF 2 ) q i— (SI)— (CF 2 ) q2 O t ⁇ r , where SI is the sulfonimide group, ql and q2 are greater than or equal to one and t is greater than or equal to zero.
  • the side chains that extend off of the backbone chains may be end-capped chains, cross-link chains, or both.
  • the end-capped chains may have at least one sulfonimide group,— S0 2 — NH— S0 2 — and may include between two and five of the sulfonimide groups or even greater than five sulfonimide groups.
  • the end- capped chains may be capped with a CF 3 group a SO 3 H group, or a portion of the side chains may be capped with CF 3 groups and another portion with SO 3 H groups.
  • the end-capped chains that are capped with CF 3 may include multiple sulfonimide groups and the portion of end-capped chains that are capped with SO 3 H may include at least one sulfonimide group.
  • the perfluorinated side chains may be the end-capped chains and 1-80% of the side chains may be the cross-link chains. In other examples, 50-99% of the perfluorinated side chains are the end-capped chains and 1- 50% of the side chains are the cross-link chains.
  • the proton exchange material has Structure 1 shown below, where the horizontal lines represent the perfluorinated carbon backbone chains, the vertical lines represent side chains, SI is sulfonimide, m is greater than or equal to one, n is greater than or equal to two, and p is greater than or equal to two.
  • the amounts of side chains and cross-link chains may be as described above.
  • the proton exchange material has Structure 2 shown below, where the horizontal lines represent the perfluorinated carbon backbone chains, the vertical lines represent side chains, SI is sulfonimide, m is greater than or equal tol, n is greater than or equal to two, and p is greater than or equal to two.
  • the amounts of side chains and cross-link chains may be as described above.
  • the proton exchange material includes perfluorinated carbon chains and proton exchange sites that are located exclusively on perfluorinated cross-links that include at least one sulfonimide group ("SI"),— S0 2 — NH— S0 2 — , where the nitrogen in the sulfonimide group is a type of proton exchange site. That is, the nitrogen atom or atoms of the sulfonimide group or groups are the only proton exchange sites within the proton exchange material.
  • the proton exchange material has Structure 3 shown below, where the backbones and cross-links are perfluorinated carbon chains and m is greater than or equal to two.
  • the cross-links have the sulfonimide structure (SO2NHSO2 (CF2)n)m, where 1 ⁇ n ⁇ 1000 and m is greater than or equal to two.
  • a user may design the proton exchange material of the disclosed examples with a selected number of sulfonimide groups within the side chains to provide a desired equivalent weight (1/mol ) of proton exchange sites (nitrogen atoms).
  • the location of the sulfonimide group or groups on cross-link chains of the proton exchange material also provides the ability to design the material with a particular equivalent weight for high proton conductivity and high resistance to solvents, such as water. For instance, the cross-linking of the perfluorinated carbon chains resists "washing out” of the sulfonimide group or groups and thereby provides resistance to water and swelling.
  • the proton exchange material has an ionic exchange capacity of more than two times that of sulfonated tetrafluoroethylene (Nafion).
  • the equivalent weight of the proton exchange material may be 700-1,000.
  • the disclosed range provides relatively high proton conductivity and a suitable rheology for membranes or other shapes that are desired for a fuel cell or other applications.
  • the sulfonimide group is a stronger acid than sulfonic acid.
  • the equivalent weight is 850-950.
  • a similar polymer with an equivalent weight below approximately 560 is a semi-solid, low molecular weight material that would not be mechanically suitable as a membrane.
  • Sulfonated tetrafluoroethylene with an equivalent weight of above approximately 1100 is a tough, solid material that has a low solubility in water or other polar solvents.
  • a user may fabricate the disclosed proton exchange material by forming a polymer having perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains, where the perfluorinated side chains include cross-link chains that have multiple sulfonimide groups,— S0 2 — NH— S0 2 — .
  • the forming includes synthesizing a perfluorinated sulfonic acid precursor and converting sulfonic acid groups,— S0 2 F, in the perfluorinated sulfonic acid precursor to amide groups,— S0 2 NH 2 .
  • the user then converts the amide groups,— S0 2 NH 2 , to the sulfonimide groups,— S0 2 — NH— S0 2 — .
  • the conversions of the amide groups to sulfonimide groups are conducted using an end-capping agent, a cross-linking agent, or both.
  • the forming includes synthesizing a perfluorinated sulfonic acid precursor, synthesizing a linear sulfonimide precursor, and cross-linking the sulfonimide precursor with the perfluorinated sulfonic acid precursor to produce the disclosed proton exchange material (target material).
  • An example of a synthesis process is shown below in Steps 1-3.
  • Target po!ymer L0029J Although a combination of features is shown in the illustrated examples, not all of them need to be combined to realize the benefits of various embodiments of this disclosure. In other words, a system designed according to an embodiment of this disclosure will not necessarily include all of the features shown in any one of the Figures or all of the portions schematically shown in the Figures. Moreover, selected features of one example embodiment may be combined with selected features of other example embodiments.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A proton exchange material includes perfluorinated carbon backbone chains and side chains extending off of the perfluorinated carbon backbone chains. The perfluorinated side chains include cross-link chains that have multiple sulfonimide groups, -SO2-NH-SO2-.

Description

PROTON EXCHANGE MATERIAL AND METHOD THEREFOR
BACKGROUND
[0001] This disclosure relates to fluoropolymers that are used as proton exchange materials in applications such as fuel cells.
[0002] Fuel cells are commonly used for generating electric current. A single fuel cell typically includes an anode catalyst, a cathode catalyst, and an electrolyte between the anode and cathode catalyst for generating an electric current in a known electrochemical reaction between a fuel and an oxidant. The electrolyte may be a fluoropolymer membrane, which is also known as a proton exchange membrane or "PEM."
[0003] One common type of fluoropolymer membrane is sulfonated tetrafluoroethylene, known as NAFION. Sulfonated tetrafluoroethylene includes proton exchange sites that function to transmit protons between the anode and cathode catalyst. The proton exchange site is at a sulfonic acid group SO3H, which terminates a pendent perfluorinated side chain of the polymer. Another common type of fluoropolymer membrane is sulfonamide which also includes proton exchange sites that function to transmit protons between the anode and cathode catalyst. The proton exchange site is at a nitrogen atom - S02-NH-S02-CF3 which terminates a pendent side chain of the polymer.
SUMMARY
[0004] A disclosed proton exchange material includes perfluorinated carbon backbone chains and side chains extending off of the perfluorinated carbon backbone chains. The side chains include cross-link chains that have multiple sulfonimide groups,— S02— NH— S02— .
[0005] An example method of fabricating a proton exchange material includes forming a polymer having perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains. The perfluorinated side chains include cross-link chains that have multiple sulfonimide groups,— S02— NH— S02— . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0006] The disclosed example proton exchange materials may be used for fuel cell proton exchange membranes or other applications where proton exchange is desirable. As will be described, the disclosed proton exchange material provides the ability to increase the number of proton exchange sites on a molar basis while maintaining resistance to solvents, such as water. As a comparison, an increase in the number of proton exchange sites in sulfonated tetrafluoroethylene increases proton conductivity but also increases solubility in water, which is detrimental in fuel cell applications. Conversely, a decrease in the number of proton exchange sites in sulfonated tetrafluoroethylene provides an increase in resistance to water but decreases proton conductivity and debits fuel cell performance.
[0007] An example proton exchange material includes perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains. The perfluorinated side chains include cross-link chains that have multiple sulfonimide groups,— S02— NH— S02— .
[0008] In embodiments, the perfluorinated carbon backbone chains have a structure of — (CF2)— . The perfluorinated side chains include a general structure of — CxF2XOz— , where X is greater than or equal to two and Z is greater than or equal to zero. For instance, the side chains have a structure— {(CF2)qi— (SI)— (CF2)q2Ot}r, where SI is the sulfonimide group, ql and q2 are greater than or equal to one and t is greater than or equal to zero.
[0009] In embodiments, the side chains that extend off of the backbone chains may be end-capped chains, cross-link chains, or both. The end-capped chains may have at least one sulfonimide group,— S02— NH— S02— and may include between two and five of the sulfonimide groups or even greater than five sulfonimide groups. Additionally, the end- capped chains may be capped with a CF3 group a SO3H group, or a portion of the side chains may be capped with CF3 groups and another portion with SO3H groups. The end-capped chains that are capped with CF3 may include multiple sulfonimide groups and the portion of end-capped chains that are capped with SO3H may include at least one sulfonimide group.
[0010] In the proton exchange material, 20-99% of the perfluorinated side chains may be the end-capped chains and 1-80% of the side chains may be the cross-link chains. In other examples, 50-99% of the perfluorinated side chains are the end-capped chains and 1- 50% of the side chains are the cross-link chains.
[0011] In one example, the proton exchange material has Structure 1 shown below, where the horizontal lines represent the perfluorinated carbon backbone chains, the vertical lines represent side chains, SI is sulfonimide, m is greater than or equal to one, n is greater than or equal to two, and p is greater than or equal to two. The amounts of side chains and cross-link chains may be as described above.
[0012] Structure 1
Figure imgf000004_0001
(SI)m-S03H (SI)n-CF3 (SI)p
[0014] In another example, the proton exchange material has Structure 2 shown below, where the horizontal lines represent the perfluorinated carbon backbone chains, the vertical lines represent side chains, SI is sulfonimide, m is greater than or equal tol, n is greater than or equal to two, and p is greater than or equal to two. The amounts of side chains and cross-link chains may be as described above.
[0015] Structure 2
Figure imgf000004_0002
(SI)m-CF3 (SI)n-CF3 (SI)p
[0017] In other embodiments, the proton exchange material includes perfluorinated carbon chains and proton exchange sites that are located exclusively on perfluorinated cross-links that include at least one sulfonimide group ("SI"),— S02— NH— S02— , where the nitrogen in the sulfonimide group is a type of proton exchange site. That is, the nitrogen atom or atoms of the sulfonimide group or groups are the only proton exchange sites within the proton exchange material. For instance, the proton exchange material has Structure 3 shown below, where the backbones and cross-links are perfluorinated carbon chains and m is greater than or equal to two.
[0018] Structure 3
Figure imgf000005_0001
(si)m (SI)m
[0020] In a further example, the cross-links have the sulfonimide structure (SO2NHSO2 (CF2)n)m, where 1 < n < 1000 and m is greater than or equal to two.
[0021] A user may design the proton exchange material of the disclosed examples with a selected number of sulfonimide groups within the side chains to provide a desired equivalent weight (1/mol ) of proton exchange sites (nitrogen atoms).
[0022] The location of the sulfonimide group or groups on cross-link chains of the proton exchange material also provides the ability to design the material with a particular equivalent weight for high proton conductivity and high resistance to solvents, such as water. For instance, the cross-linking of the perfluorinated carbon chains resists "washing out" of the sulfonimide group or groups and thereby provides resistance to water and swelling. In some examples, the proton exchange material has an ionic exchange capacity of more than two times that of sulfonated tetrafluoroethylene (Nafion).
[0023] The equivalent weight of the proton exchange material may be 700-1,000. The disclosed range provides relatively high proton conductivity and a suitable rheology for membranes or other shapes that are desired for a fuel cell or other applications. Moreover, the sulfonimide group is a stronger acid than sulfonic acid. In a further example, the equivalent weight is 850-950. As a comparison, a similar polymer with an equivalent weight below approximately 560 is a semi-solid, low molecular weight material that would not be mechanically suitable as a membrane. Sulfonated tetrafluoroethylene with an equivalent weight of above approximately 1100 is a tough, solid material that has a low solubility in water or other polar solvents. [0024] A user may fabricate the disclosed proton exchange material by forming a polymer having perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains, where the perfluorinated side chains include cross-link chains that have multiple sulfonimide groups,— S02— NH— S02— . As an example, the forming includes synthesizing a perfluorinated sulfonic acid precursor and converting sulfonic acid groups,— S02F, in the perfluorinated sulfonic acid precursor to amide groups,— S02NH2. The user then converts the amide groups,— S02NH2, to the sulfonimide groups,— S02— NH— S02— . Depending on the desired structure of the proton exchange material, the conversions of the amide groups to sulfonimide groups are conducted using an end-capping agent, a cross-linking agent, or both.
[0025] In other examples, the forming includes synthesizing a perfluorinated sulfonic acid precursor, synthesizing a linear sulfonimide precursor, and cross-linking the sulfonimide precursor with the perfluorinated sulfonic acid precursor to produce the disclosed proton exchange material (target material). An example of a synthesis process is shown below in Steps 1-3.
[0026] Step 1. c¾ =cf¾ + α¾=θ Free radical C¾-CF¾¾-CF-^ »
[0027] Step 2.
^ FSOs-iGF ii SSCiNHSOriCFjpJis - SO.F
[0028] Step 3.
Target po!ymer
Figure imgf000006_0001
L0029J Although a combination of features is shown in the illustrated examples, not all of them need to be combined to realize the benefits of various embodiments of this disclosure. In other words, a system designed according to an embodiment of this disclosure will not necessarily include all of the features shown in any one of the Figures or all of the portions schematically shown in the Figures. Moreover, selected features of one example embodiment may be combined with selected features of other example embodiments.
[0030] The preceding description is exemplary rather than limiting in nature. Variations and modifications to the disclosed examples may become apparent to those skilled in the art that do not necessarily depart from the essence of this disclosure. The scope of legal protection given to this disclosure can only be determined by studying the following claims.

Claims

CLAIMS What is claimed is:
1. A proton exchange material comprising:
perfluorinated carbon backbone chains; and
side chains extending off of the perfluorinated carbon backbone chains, the side chains including cross-link chains that have multiple sulfonimide groups,— S02— NH— S02— .
2. The proton exchange material as recited in claim 1, wherein the side chains include end-capped chains that have at least one sulfonimide group,— S02— NH— S02— .
3. The proton exchange material as recited in claim 2, wherein the end-capped chains include between two and five sulfonimide groups.
4. The proton exchange material as recited in claim 2, wherein 20-99% of the side chains are the end-capped chains and 1-80% of the side chains are the cross-link chains.
5. The proton exchange material as recited in claim 2, wherein 50-99% of the side chains are the end-capped chains and 1-50% of the side chains are the cross-link chains.
6. The proton exchange material as recited in claim 2, wherein a portion of the end- capped chains are capped with CF3 and another portion of the end-capped chains are capped with SO3H.
7. The proton exchange material as recited in claim 6, wherein the end-capped chains that are capped with CF3 include multiple sulfonimide groups and the portion of end-capped chains that are capped with SO3H include at least one sulfonimide group.
8. The proton exchange material as recited in claim 2, wherein the end-capped chains are capped with CF3.
9. The proton exchange material as recited in claim 2, wherein the end-capped chains are capped with SO3H.
10. The proton exchange material as recited in claim 1, wherein the side chains include between two and five sulfonimide groups.
11. The proton exchange material as recited in claim 1, wherein any proton exchange sites are located exclusively on the cross-link chains.
12. The proton exchange material as recited in claim 1, comprising an equivalent weight (1/mol ) of 700 - 1,000 with regard to the proton exchange sites.
13. The proton exchange material as recited in claim 12, wherein the equivalent weight is 850-950.
14. A method of fabricating a proton exchange material, comprising:
forming a polymer having perfluorinated carbon backbone chains and perfluorinated side chains extending off of the perfluorinated carbon backbone chains, the side chains including cross-link chains that have multiple sulfonimide groups,— S02— NH— S02— .
15. The method as recited in claim 14, wherein the forming includes synthesizing a perfluorinated sulfonic acid precursor and converting sulfonic acid groups,— S02F, in the perfluorinated sulfonic acid precursor to amide groups,— S02NH2.
16. The method as recited in claim 15, wherein the forming includes converting the amide groups,— S02NH2, to the sulfonimide groups,— S02— NH— S02— .
17. The method as recited in claim 14, wherein the forming of the polymer includes synthesizing a perfluorinated sulfonic acid precursor, synthesizing a linear sulfonimide precursor, and cross-linking the perfluorsulfinated sulfonic acid precursor with the sulfonimide precursor to produce the polymer.
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WO2014098912A1 (en) 2012-12-21 2014-06-26 United Technologies Corporation Proton exchange material and method therefor
WO2015020630A1 (en) * 2013-08-06 2015-02-12 United Technologies Corporation Method for fabricating electrolyte membrane using in-situ cross-linking
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