IP Library › Granted Patent US 12,344,942
Granted Patent B2
US 12,344,942 · App. 17/590,971 · Granted Jul 1, 2025

Proton exchange membrane water electrolyzer membrane electrode assembly

Inventors: Fan Yang (Latham, NY); Chao Lei (Latham, NY); Arthur Griffith (Latham, NY); Robert Stone (Latham, NY); Cortney Mittelsteadt (Latham, NY)
Assignee: PLUG POWER INC.
C25B1/04C25B9/19C25B11/053C25B11/081C25B13/02C25B13/08
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Quick Facts
Patent No.
US 12,344,942
App. No.
17/590,971
Granted
Jul 1, 2025
Kind
B2
Abstract

An exchange membrane includes, for example, a first layer membrane having a first thickness, a second layer membrane having a thickness less than the first thickness, and the second layer membrane containing a catalyst, a catalyst content in the second layer membrane being greater than a catalyst content in the first layer membrane, and the exchange membrane having an interface between the first layer membrane and the second layer membrane. In some embodiments, the membrane electrode assembly (MEA) includes the first layer membrane without a catalyst, and/or the exchange membrane includes a bi-layer exchange membrane.

Claims (34)

1. A exchange membrane consisting of:

a first layer membrane having a first thickness;

a second layer membrane disposed directly on the first layer membrane, the second layer membrane having a thickness less than the first thickness, and the second layer membrane containing a mixture of a nanoparticle catalyst and an ionomer, the catalyst disposed throughout the thickness of the second layer membrane, a catalyst content in the second layer membrane being greater than a catalyst content in the first layer membrane;

the exchange membrane having an interface between the first layer membrane and the second layer membrane, wherein the first layer membrane and the second layer membrane contact each other at the interface;

the first layer membrane laminated to the second layer membrane to define a laminated bi-layer exchange membrane;

the bi-layer exchange membrane operable to allow the passage of cations;

wherein the bi-layer exchange membrane is operable in an membrane electrode assembly (MEA) upon application of an electrical supply to an anode electrode and a cathode electrode to conduct protons through the exchange membrane to electrolyze and split water into oxygen and hydrogen; and

wherein the laminated exchange membrane is disposed on a roll.

2. The exchange membrane of claim 1 wherein the first layer membrane does not include any catalyst.

3. The exchange membrane of claim 1 wherein the first layer membrane comprises an ionomer and does not include any catalyst.

4. The exchange membrane of claim 1 wherein the second layer membrane comprises the catalyst comprising platinum (Pt).

5. The exchange membrane of claim 1 wherein the exchange membrane comprises 1 percent of the catalyst by weight.

6. The exchange membrane of claim 1 wherein the first layer membrane comprises an ionomer and the second layer membrane comprises the catalyst comprising platinum (Pt).

7. The exchange membrane of claim 1 wherein the first layer membrane comprises a thickness of at least 1.5 mil to 2 mil, and the second layer membrane comprises a thickness of 1 mil to 1.5 mil.

8. The exchange membrane of claim 1 wherein the second layer membrane comprises the catalyst disposed uniformly throughout the thickness of an ionomer.

9. The exchange membrane of claim 1 wherein the catalyst comprises a platinum (Pt) nanoparticle catalyst.

10. A bi-layer membrane electrode assembly (MEA) consisting of:

a first layer membrane having a first thickness;

a second layer membrane disposed directly on the first layer membrane, the second layer membrane having a thickness less than the first thickness, and the second layer membrane containing a mixture of a nanoparticle catalyst and an ionomer, the catalyst disposed throughout the thickness of the second layer, the catalyst content in the second layer membrane being greater than a catalyst content in the first layer membrane;

the first layer membrane and the second layer membrane defining an exchange membrane having an interface between the first layer membrane and the second layer membrane wherein the first layer membrane and the second layer membrane contact each other at the interface;

the exchange membrane operable to allow the passage of cations;

an anode electrode disposed directly on the second layer membrane;

a cathode electrode disposed directly on the first layer membrane; and

wherein the bi-laver membrane electrode assembly (MEA) upon application of an electrical supply to the anode electrode and to the cathode electrode conducts protons through the exchange membrane to electrolyze and split water into oxygen and hydrogen.

11. The membrane electrode assembly (MEA) of claim 10 wherein the first layer membrane does not include any catalyst.

12. The membrane electrode assembly (MEA) of claim 10 wherein the second layer comprises a casted layer.

13. The membrane electrode assembly (MEA) of claim 10 wherein the first layer membrane comprises an ionomer and does not include any catalyst.

14. The membrane electrode assembly (MEA) of claim 10 wherein the exchange membrane comprises a laminated exchange membrane.

15. The membrane electrode assembly (MEA) of claim 10 wherein the second layer membrane comprises the catalyst comprising platinum (Pt).

16. The membrane electrode assembly (MEA) of claim 10 wherein the exchange membrane comprises 1 percent of the catalyst by weight.

17. The membrane electrode assembly (MEA) of claim 10 wherein the first layer membrane comprises an ionomer and the second layer membrane comprises the catalyst comprising platinum (Pt).

18. The membrane electrode assembly (MEA) of claim 10 wherein the first layer membrane comprises a thickness of at least 1.5 mil to 2 mil, and the second layer membrane comprises a thickness of 1 mil to 1.5 mil.

19. The membrane electrode assembly (MEA) of claim 10 wherein the second layer membrane comprises the catalyst disposed uniformly throughout the thickness of an ionomer.

20. The membrane electrode assembly (MEA) of claim 10 wherein the catalyst comprises a platinum (Pt) nanoparticle catalyst.

Assignments (3)
RELEASE OF SECURITY INTEREST Recorded Nov 25, 2025
From: YA II PN, LTD., IN ITS CAPACITY AS COLLATERAL AGENT
To: PLUG POWER, INC.; PLUG POWER HYDROGEN HOLDINGS, INC.; UNITED HYDROGEN GROUP INC.; PLUG PROJECT HOLDING CO., LLC; PEACHTREE RENEWABLES, LLC; JOULE PROCESSING LLC; APPLIED CRYO TECHNOLOGIES, INC.; ALLOY CUSTOM PRODUCTS, LLC; HYPULSION U.S. HOLDING, INC.
Reel/Frame 073036/0448 →
SECURITY INTEREST Recorded Apr 28, 2025
From: PLUG POWER INC.; APPLIED CRYO TECHNOLOGIES, INC.; PLUG POWER HYDROGEN HOLDINGS, INC.; UNITED HYDROGEN GROUP INC.; ALLOY CUSTOM PRODUCTS, LLC; JOULE PROCESSING LLC; PEACHTREE RENEWABLES, LLC; PLUG PROJECT HOLDING CO., LLC; HYPULSION U.S. HOLDING, INC.
To: YA II PN, LTD., IN ITS CAPACITY AS COLLATERAL AGENT
Reel/Frame 071084/0264 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 24, 2022
From: YANG, FAN; LEI, CHAO; GRIFFITH, ARTHUR; STONE, ROBERT; MITTELSTEADT, CORTNEY
To: PLUG POWER INC.
Reel/Frame 060883/0738 →
Continuity (2)
Provisional Application 63144539 · Feb 2, 2021
Related Publication 20220243344A1 · Aug 4, 2022
References Cited (70)
US 6500217B1 · Starz et al. · 2002 [cited by applicant]
US 6696190B2 · Haridoss · 2004 [cited by applicant]
US 7132188B2 · Masel et al. · 2006 [cited by applicant]
US 7691507B2 · Ballantine · 2010 [cited by applicant]
US 8962132B2 · Liu et al. · 2015 [cited by applicant]
US 11124885B2 · Xu et al. · 2021 [cited by applicant]
US 20020058172A1 · Datz et al. · 2002 [cited by applicant]
US 20040023105A1 · Hohenthanner et al. · 2004 [cited by applicant]
US 20050053818A1 · St-Arnaud et al. · 2005 [cited by applicant]
US 20150290594A1 · Van Berchum · 2015 [cited by examiner]
US 20150322578A1 · Wakabayashi et al. · 2015 [cited by applicant]
US 20150368817A1 · Xu et al. · 2015 [cited by applicant]
US 20170317370A1 · Kang et al. · 2017 [cited by applicant]
US 20170321334A1 · Kuhl et al. · 2017 [cited by applicant]
US 20180062192A1 · Capuano et al. · 2018 [cited by applicant]
US 20190134570A1 · Pintauro et al. · 2019 [cited by applicant]
US 20190296364A1 · Nakano · 2019 [cited by examiner]
US 20200099061A1 · Price et al. · 2020 [cited by applicant]
US 20200102660A1 · Lewinski et al. · 2020 [cited by applicant]
US 20200240023A1 · Cave et al. · 2020 [cited by applicant]
US 20210305598A1 · Hamdan et al. · 2021 [cited by applicant]
US 20210384540A1 · Mistry et al. · 2021 [cited by applicant]
US 20210395908A1 · Kuhl et al. · 2021 [cited by applicant]
US 20220216494A1 · Minamibayashi · 2022 [cited by examiner]
US 20220243339A1 · Yang et al. · 2022 [cited by applicant]
US 20220243344A1 · Yang et al. · 2022 [cited by applicant]
CN 101463487A · 2009 [cited by applicant]
EP 2927998A1 · 2015 [cited by applicant]
FR 2624885 · 1998 [cited by applicant]
JP 2006107914A · 2006 [cited by applicant]
KR 1020080090079A · 2008 [cited by applicant]
KR 102291160B1 · 2021 [cited by applicant]
WO 2015193211A1 · 2015 [cited by applicant]
WO 2016048309A1 · 2016 [cited by applicant]
WO 2022169844A1 · 2022 [cited by applicant]
WO 2022169851A1 · 2022 [cited by applicant]
Klose et al (“Membrane Interlayer with Pt Recombination Particles for Reduction of the Anodic Hydrogen Content in PEM Water Electrolysis”, Journal of The Electrochemical Society, 165, 16, 2018, pp. F1271-F1277) (Year: 2… [cited by examiner]
Li et al (“Bilayer Anion-Exchange Membrane with Low Borohydride Crossover and Improved Fuel Efficiency for Direct Borohdyride Fuel Cell”, ACS Appl. Mater. Interfaces 2020, 12, 27184-27189) (Year: 2020). [cited by examiner]
Liu et al (“The use of polypyrrole modified carbon-supported cobalt hydroxide as cathode and anode catalysts for the direct borohydride fuel cell”, Journal of Power Sources 192 (2009) 385-390). (Year: 2009). [cited by examiner]
Guella et al (“Kinetic Features of the Platinum Catalyzed Hydrolysis of Sodium Borohydride from 11B NMR Measurements”, J. Phys . Chem. C 2007, 111, 18744-18750) (Year: 2007). [cited by examiner]
Qin (“Introducing catalyst in alkaline membrane for improved performance direct borohydride fuel cells”, Journal of Power Sources 374 (2018) 113-120) (Year: 2018). [cited by examiner]
Abdu et al (“Catalytic Polyelectrolyte Multilayers at the Bipolar Membrane Interface”, ACS Appl. Mater. Interfaces, 2013, 5, 10445-10455). (Year: 2013). [cited by examiner]
Membrane Interlayer with Pt Recombination Particles for Reduction of the Anodic Hydrogen Content in PEM Water Electrolysis, Journal of The Electrochemical Society, 165 (16) F1271-F1277 (2018). [cited by applicant]
Yang et al., Notification of Transmittal, International Search Report and Written Opinion for PCT/US 2022/014914 titled “Proton Exchange Membrane Water Electrolyzer Membrane Electrode Assembly”, 9 pages, dated May 12, 2… [cited by applicant]
Yang et al., Notification of Transmittal, International Search Report and Written Opinion for PCT/US 2022/014905 titled “Proton Exchange Membrane Water Electrolyzer Membrane Electrode Assembly”, 9 pages, dated May 12, 2… [cited by applicant]
C. Klose, et al., Membrane Interlayer with Pt Recombination Particles for Reduction of the Anodic Hydrogen Content in PEM Water Electrolysis, Journal of The Electrochemical Society, 165 (16) F1271-F1277, 2018. [cited by applicant]
Fan Yan, Chao Lei, Arthur Griffith, Robert Stone and Cortney Mittlesteadt, U.S. Appl. No. 17/590,969, filed Feb. 2, 2022, entitled “Proton Exchange Membrane Water Electrolyzer Membrane Electrode Assembly”. [cited by applicant]
Mittelsteadt et al., International Patent Application PCT/US223/076844, entitled “Recombination Layers for Crossover Mitigation for Exchange Membranes and Water Electrolyzer Membrane Electrode Assemblies,” filed on Oct.… [cited by applicant]
Mittelsteadt et al., International Search Report and Written Opinion for PCT/US2023/076844, entitled “Recombination Layers for Crossover Mitigation for Exchange Membranes Andwater Electrolyzer Membrane Electrode Assembl… [cited by applicant]
“Unfolding the Complex Relations between Morphology, Viscoeleastic Properties, Hydration Behavior and (Proton, Water) Transport in Poly-Electrolytes and Ionomers such as NAFION®,” Max Planck Institute for Solid State Re… [cited by applicant]
Stahler et al., “Scalable Implementation of Recombination Catalyst Layers to Mitigate Gas Crossover in PEM Water Electrolyzers,” Journal of The Electrochemical Society, 169, 034522, 9 pages, Mar. 21, 2022. [cited by applicant]
Millet et al., “Precipitation of Metallic Platinum into Nafion Ionomer Membranes,” J. Electrochem. Soc., vol. 140, No. 5, pp. 1373-1380, May 1993. [cited by applicant]
Shin et al., “Improving the Mechanical Durability of Short-Side-Chain Perfluorinated Polymer Electrolyte Membranes by Annealing and Physical Reinforcement,” ACS Omega 2019, 4, 19153-19163, 11 pages, 2019. [cited by applicant]
Sode et al., “Controlling the deposition of Pt nanoparticles within the surface region of Nafion,” Journal of Membrane Science, vol. 376, Issues 1-2, pp. 162-169, abstract, highlights, introduction, 6 pages, Jul. 2011. [cited by applicant]
Klaus-Dieter Kreuer and Giuseppe Portale, “A Critical Revision of the Nano-Morphology of Proton Conducting Ionomers and Polyelectrolytes for Fuel Cell Applications,” Adv. Funct. Mater. 2013, 23, 5390-5397, 8 pages, 2013. [cited by applicant]
Kreuer et al., “Short-side-chain proton conducting perfluorosulfonic acid ionomers: Why they perform better in PEM fuel cells,” Journal of Power Sources 178 (2008) 499-509, 11 pages, 2008. [cited by applicant]
Kreuer, “On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells,” Journal of Membrane Science 185 (2001) 29-39, 11 pages, 2001. [cited by applicant]
Melchior et al., “About the Interactions Controlling Nafion's Viscoelastic Properties and Morphology,” Macromolecules 2015, 48, 8534-8545, 12 pages, 2015. [cited by applicant]
Kreuer, “The role of internal pressure for the hydration and transport properties of ionomers and polyelectrolytes,” Solid State Ionics 252 (2013) 93-101, 12 pages, 2013. [cited by applicant]
Kreuer et al., “Membrane Materials for PEM-Fuel-Cells: A Microstructural Approach,” available In Proton Conducting Membrane Fuel Cells I, edited by Landgrebe et al, vol. PV 95-23, The Electrochemical Society, Pennington… [cited by applicant]
Yang et al., Partial Supplemental European Search Report, European Patent Application N22750305.9, 15 pages, Feb. 18, 2025. [cited by applicant]
Leddy et al. (“Density and Solubility of Nation: Recast, Annealed, and Commercial Films”, Anal. Chem., 1996, 68, 3793-3796), 4 pages, (Year: 1996). [cited by applicant]
Mirsherkari et al. (“High performance and cost-effective membrane electrode assemblies for advanced proton exchange membrane water electrolyzes: Long-term durability assessment,” Int. J. Hydrogen Energy 2021, 46, 1526-1… [cited by applicant]
Yang et al. (“Operation of thin Nation-based self-humidifying membranes in proton exchange membrane fuel cells with dry H2 and 02,” J. Power Sources 2004, 139, 170-175), 6 pages, (Year: 2005). [cited by applicant]
Chen et al. (“High-rate roll-to-roll stack and lamination of multilayer structured membrane electrode assembly,” J. Manuf. Process. 2016, 23, 175-182), 8 pages, (Year: 2016). [cited by applicant]
Nation Product Bulletin P-14: Chemours Published in 2020, 2 pages, (Year: 2020). [cited by applicant]
Park et al. (“Roll-to-roll production of catalyst coated membranes for low-temperature electrolyzers,” J. Power Sources 2020, article 228819, pages 1-9), 9 pages, (Year: 2020). [cited by applicant]
Stahler et al. (“A completely slot die coated membrane electrode assembly,” Int. J. Hydrogen Energy 2019, 44, 7053-7058), 6 pages, (Year: 2019). [cited by applicant]
Du et al. (“Effects of ionomer and dispersion methods on the rheological behavior of proton exchange membrane fuel cell catalyst ink,” Int. J. Hydrogen Energy 2020, 45(53), 29430-29441), 12 pages, (Year: 2020). [cited by applicant]
Yang et al, First Office Action for U.S. Appl. No. 17/590,969, mailed April 3, 2025, 30 pages. 30 pages, April 3, 2025. [cited by applicant]