Workshop on Ion Exchange Membranes for Energy Applications – EMEA2018

26th – 28th June 2018 in Bad Zwischenahn (Germany)

60 participants from 15 countries made the last EMEA-workshop in June 2017 a success. The coming EMEA2018 Workshop will be the 6th workshop in this series. Material developments and ion exchange membrane based systems for energy applications will be discussed by representatives from research and industry with the focus set on anion exchange membranes. In addition to invited and contributed talks, the workshop features a panel discussion, in which experts from academia and industry will discuss the development of the field. A poster exhibition offers scientists and especially young researchers and students the opportunity to present their work. A price for the best poster will be awarded. A guided tour through the DLR Institute of Networked Energy Systems (former NEXT ENERGY) research laboratories, a get-together and a conference dinner will provide additional opportunities for lively scientific exchange in a familiar atmosphere.

AGENDA

Tuesday June 26th

20:00 | Get-together

Wednesday June 27th

8:30 | Opening Reception Desk

9:00 | Welcome

9:15 | Session 1

       

 

 

 

Polyimidazolium Anion Exchange Membranes

Steven Holdcroft, Jiantao Fan, Andrew G. Wright, Benjamin Britton, Thomas Weissbach, Thomas J. G. Skalski, Jonathan Ward, Timothy J. Peckham, Eric Schibli+, Barbara Frisken+

Simon Fraser University
Department of Chemistry, Department of Physics+,  8888 University Drive, Burnaby, Greater Vancouver, BC, V5A 1S6, Canada
holdcrof@sfu.ca

 

Cationic polyelectrolytes possess cationic groups as either a pendent functionality or integral to the main chain. In recent years, the study of cationic polymers possessing hydroxide counter ions have gained prominence. However, organic-based polymer cations are prone to nucleophilic attack by hydroxide ions, destroying the anion-exchange capacity and hydroxide ion conductivity. Numerous cationic head groups are being explored with a view to increasing the stability of cationic polymers in highly basic media. Despite rapid advancements, cationic polymers stable in caustic solutions at elevated temperatures have proved elusive.

In this presentation, we report on poly(arylene-imidazoliums), which were synthesized by microwave polycondensation of dialdehyde with bisbenzil and quantitatively functionalized by alkylation. This cationic polyelectrolyte is sterically protected around the C2-position and possesses a t1/2 of >5000 h in 10 M KOHaq at 100 ˚C. Alkaline stability is rationalized through analyses of model compounds, single crystal x-ray diffraction, and density functional theory. The polyelectrolytes form tough, pliable, transparent, anionically conductive films.

 

10:15 | Poster Presentation with Coffee and Snacks

10:45 | Session 2

Creating Co-continuous Morphologies in Polymers for Anion Exchange Membranes

Frededrick L Beyer

U.S. Army Research Laboratory
Aberdeen Proving Ground, Maryland, USA
frederick.l.beyer3.civ@mail.mil

 

Anion exchange membranes (AEMs) for use in alkaline fuel cells (AFCs) generally suffer from a combination of shortcomings in conductivity, durability, dimensional stability, and chemical stability. In this program, we have explored a strategy to address three of these requirements simultaneously through control of morphological behavior. Morphological behavior, including form, orientation, and continuity, is expected to have significant effects on conductivity. We seek to create materials that have co-continuous morphologies combining charged, hydrophilic domains for charge transport, and rigid hydrophobic domains for mechanical reinforcement and dimensional stability. Using trimethylamine as a model cation, reaction-induced phase separation was used to create polymer films with co-continuous morphologies and tunable mechanical behavior. This process generates a crosslinked, microphase separated film in one step through the reaction of copolymer of cationic block and a norbornene-functionalized block is reacted with cyclooctene (CO) and dicyclopentadiene (DCPD) to create. The resulting films were found to have excellent conductivity and reasonable mechanical properties. Mechanical properties can be modified by adjusting the relative amounts of CO and DCPD, and by adjusting the molecular weight of the cation-containing block copolymer. Subsequent efforts to improve mechanical properties and chemical stability, as required for device lifetimes, will also be described.

12:15 | Lunch

13:45 | Guided Tour through the Laboratories of the DLR Institute of Networked Energy Systems, Oldenburg

16:00 | Session 3

Technical Targets for Membranes in Alkaline Electrolysis: Translating ex-situ Properties into in-situ Performance

Dr. Artjom Maljusch, Oliver Conradi, Patrick Borowski

Evonik Creavis GmbH
Paul-Baumann-Str. 1, 45772 Marl
artjom.maljusch@evonik.com

 

With the transformation from fossil-based energy generation to renewables, electrolytic hydrogen will play a key role. One limiting factor to widespread adoption of electrolysis for hydrogen production and energy storage are the specific investment costs of PEM-based systems. However, membrane electrolysis under alkaline operation enables elimination of expensive components while keeping many operational advantages of PEM systems. Even though the research efforts on OH-conducting polymers and membranes have been increased significantly in recent years there is still no concept with commercial maturity.

This presentation wants to derive some generic design rules and performance indicators how to translate intrinsic membrane properties systematically into in-situ performance. This holistic approach can provide a guideline for both academics and industry to better synchronize materials development with system requirements and vice versa.

MnO2 as effective OER catalyst for Alkaline Anion Exchange Membrane Electrolysers

Mohamed Mamlouk*, Gaurav Gupta

Newcastle University
Newcastle upon Tyne, United Kingdom- NE1 7RU
mohamed.mamlouk@ncl.ac.uk

Hydrogen is a promising fuel and energy storage solution,  due to its highly efficient conversion between H2 and electricity and good energy density in comparison to most batteries. However, 95 % of the hydrogen is generated from non-renewable sources and 5% from electrolysis due to high cost of these systems[1,2]. Around 50% of the cost of the electrolyser system comes from the precious metal catalyst used in proton exchange membrane system due to acidic environment[3,4]. However, if alkaline anion exchange membrane water electrolyser AAEMWE is used, non-precious metal can be used for catalyst, flow fields and bipolar plates, reducing the cost significantly. It is estimated that replacement of PEM electrolysers wth AAEM electrolysers offers a 43% reduction in cell stack [5]

Oxygen evolution reaction (OER) catalysts which is the slowest of the reaction in the electrolyser systems and thus require more attention. Higher performances can be achieved using high alkaline concentration feed but this in turn reduces the lifetime of the system due to degradation of AEM membrane/ionomers. Thus in order to reduce the degradation and improve the lifetime, low alkaline concentration should be used as feed solution for AEMWE i.e. deionised water. We have shown previously [4] that a current density of 100 mA cm-2 at 1.65V using NiCo2O4 for OER could be achieved at 60 °C [4]. The current research is focused on MnO2 as very effective OER catalyst in the alkaline anion exchange membrane electrolyser. The catalyst has been characterized using XRD and SEM. Using low cost LDPE based membranes radiation grafted AEM, a very promising performance electrolyser was obtained of 1.57 V at 100 mA cm-2 and  a current density of 1 A cm-2 at a potential of 1.78 V in 0.01 M NaOH at 60 °C (Figure 1).

 

Figure 1: Polarisation curve of MnO2 in 0.01 M NaOH solution at different temperature.

 

References:

[1]                  Y. Cheng, S. P. Jiang, Progress in Natural Science: Materials International 2015, 25.

[2]                  M. N. Manage, D. Hodgson, N. Milligan, S. J. R. Simons, D. J. L. Brett, International Journal of Hydrogen Energy 2011, 36.

[3]                  S. Satyapal, C. Ainscough, D. Peterson, E. Miller, in Hydrogen Production Cost from PEM Electrolysis, DOE Hydrogen and Fuel Cells Program Record, Department of Energy, United States of America, 2014.

[4]                  G. Gupta, K. Scott, M. Mamlouk, Journal of Power Sources 2018, 375, 387.

[5]                  http://www.itm-power.com/wp-content/uploads/2012/04/CaseStudy4-ReducingCostOfHydrogenProduction.pdf

17:10 | Poster Presentation with Coffee and Snacks

17:30 | Session 4

Amphoteric Membranes with Bilayer Architecture for
Vanadium Redox Flow Batteries

Lorenz Gubler1, Fabio J. Oldenburg1, Thomas J. Schmidt1,2

1 Electrochemistry Laboratory, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
2 Laboratory of Physical Chemistry, ETH Zürich, 8093 Zürich, Switzerland
lorenz.gubler@psi.ch

 

Redox-flow batteries are electrochemical energy storage devices aimed at grid-scale applications, for instance for time-shifting storage. They comprise an electrochemical converter and an external tank to store the electrolytes containing redox-active species. The all-vanadium redox flow battery (VFB) uses vanadium-ions in different oxidation states as redox-active species in the two electrolytes, thus irreversible contamination of electrolytes by cross-mixing is avoided. Nevertheless, transfer of vanadium ions across the membrane is to be avoided to minimize faradaic losses. Moreover, dissimilar rates of crossover of the 4 vanadium species can lead to electrolyte imbalance and, thus, capacity fading of the battery.

Here, we present a bilayer membrane concept consisting of Nafion® 212 that is laminated with a thin layer of meta-polybenzimidazole (mPBI). In the sulfuric acid based electrolyte of the VFB, the benzimidazole units of the PBI are protonated, thus forming an anion exchange polymer. The resulting membrane therefore has amphoteric character. Amphoteric membranes have previously shown to have promising properties for VFBs [1], combining the advantages for cation exchange and anion exchange membranes. The net vanadium transfer in this type of ionomer membrane is much more balanced (Figure 1) compared to pure cation or anion exchange membranes and, as a result, the capacity fading can be significantly reduced. Depending on the current density, the net vanadium flux across the membrane can be completely suppressed.

 

Figure 1, Left: Net vanadium flux (– ® +) over 50 charge/discharge cycles across bilayer Nafion® NR212 / PBI membranes with different PBI-layer thickness at various current densities (40, 80, 120 and 160 mA∙cm-2). Right: Schematic illustration of the Nafion-PBI bilayer membrane.

Reference:
1. F.J. Oldenburg, T.J. Schmidt, L. Gubler, J. Power Sources 368 (2017) 68

18:30 | Break

19:00 | Conference Dinner

Thursday June 28th

9:00 | Session 5

10:30 | Poster Presentation with Coffee and Snacks

11:00 | Panel Discussion

  • Moderation:
    Dr. Alexander Dyck
    (DLR Institute of Networked Energy Systems, Germany)

 12:15 | Lunch

13:45 | Session 6

Catalysts, Membranes, CO2 and Water: Requirements and Pathways for High Performing AEMFCs

William Mustain

Department of Chemical Engineering, University of South Carolina
301 Main Street; Columbia, SC 29208
mustainw@mailbox.sc.edu

 

In recent years, advances in alkaline exchange membrane fuel cells (AEMFCs) with anion exchange membrane (AEM) solid polymer electrolytes have gained traction due to their distinct – and potentially game-changing – advantages over proton exchange membrane fuel cells.  However, AEMs and AEMFCs are at a significantly less mature stage in their developmental than proton exchange membrane fuel cells (PEMFCs), and have experienced limitations specifically in the area of stability, carbonation, and achievable current and power densities, exhibiting a sizable performance gap vs PEMFCs.  This talk will focus on several fundamental and engineering advances that have enabled the creation of AEMFCs that are able to achieve ca. 2 W∙cm-2 peak power and 100’s of hours of stable operation, bringing AEMFCs much closer to the incumbent PEMFC technology, and opening the way to overcome the cost and reliability barriers that have slowed the growth and large scale market implementation of AEMFCs.

The three largest challenges facing AEMFCs today are: 1) understanding and controlling the water distribution in operating AEMFCs.  Water dynamics in these cells will be a primary theme of this presentation; 2) mitigating the negative influence of carbonation from atmospheric CO2 when using air as the oxidant.  The carbonate/bicarbonate formation and self-purging mechanisms will be discussed; and 3) reducing the platinum group metal (PGM) loading in the catalyst layers.  Strategies that included both PGM-free and low PGM (~0.1 mg∙cm-2) catalyts will be explored.  The overarching goal of this talk is not only to show the audience the state-of-the-art is in the field, but to also talk them through the mentality of our group in solving these problems and to provide some guidance regarding the approaches that have shown the most promise to date.

For more information about this project and the rest of our group, please visit https://www.mustainlab.com

15:15 | Poster Presentation with Coffee and Snacks

15:45 | Session 7

Robust Hydroxide Ion Conducting Aromatic Polymer Electrolyte Membranes

Chulsung Bae

Department of Chemistry & Chemical Biology, Rensselaer Polytechnic Institute
110 8th Street, Troy, New York, USA
baec@rpi.edu

 

A variety of energy storage and conversion electrochemical devices, such as polymer electrolyte membrane fuel cells, redox flow batteries, and water electrolysis, rely on ion-conducting polymer electrolyte membranes to separate and transport ions between the anode and cathode.1-3  Among these membranes, anion exchange membranes (AEMs) continue to receive increased attention because of their advantages of fast liquid fuel oxidation reaction in alkaline media, efficient water management, and the ability to use non-precious metal electrocatalysts for oxygen reduction reaction.4-6  Additionally, AEM-based electrochemical devices (as opposed to the liquid alkaline system) prevent leakage of corrosive fuels and carbonate precipitation.5,7  However, the most significant challenges currently preventing the advancement of AEMs in clean energy conversion technology are their poor chemical and mechanical stabilities under strong alkaline environment and low anion conductivity.  It is generally recognized that the stability of both polymer backbone and cation functional group play a crucial role in device durability.

In first part of the presentation, a chemically stable and elastomeric triblock copolymer, polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS), was functionalized with various benzyl- and alkyl-substituted quaternary ammonium (QA) groups for anion exchange membrane (AEM) fuel cell applications.  Synthetic methods involving transition metal-catalyzed C–H borylation and Suzuki coupling were utilized to incorporate six different QA structures to the polystyrene units of SEBS.  Changes in AEM properties as a result of different QA moieties and chemical stability under alkaline conditions were investigated.  Anion exchange polymers bearing the trimethyl ammonium pendants, the smallest QA cation moiety, exhibited the most significant changes in water uptake and block copolymer domain spacing to offer best ion transport properties.  It was demonstrated that incorporating stable cation structures to a polymer backbone comprising solely of C–H and C–C bonds resulted in AEM materials with improved long-term alkaline stability.  After 4 weeks in 1M NaOH at 60 °C and 80 °C, all six SEBS-QA AEMs remained chemically stable.  Fuel cell tests using benzyltrimethylammonium-containing SEBS (SEBS-TMA) as an AEM demonstrated excellent performance, generating one of the best maximum power density and lowest ohmic resistance with low Pt catalyst loaded electrode reported thus far.  Both polymer backbone and cation functional group remained stable after 110 h lifetime test at 60 °C.

In second part of the presentation, high molecular weight, quaternary ammonium-tethered poly(biphenyl alkylene)s without alkaline labile C–O bonds were synthesized via acid-catalyzed polycondensation reactions for the first time. Ion-exchange capacity was conveniently controlled by adjusting the feed ratio of two ketone monomers in the polymerization. The resultant anion exchange membranes showed high hydroxide ion conductivity up to 120 mS/cm and excellent alkaline stability at 80 °C. This study provides a new synthetic strategy for the preparation of anion exchange membranes with robust fuel cell performance and excellent stability.

References

(1)  Li, N.; Guiver, M. D. Macromolecules 2014, 47, 2175.

(2)  Hickner, M. A.; Herring, A. M.; Coughlin, E. B. J. Polym. Sci. Pol. Phys. 2013, 51, 1727.

(3)  Varcoe, J. R.; Atanassov, P.; Dekel, D. R.; Herring, A. M.; Hickner, M. A.; Kohl, P. A.; Kucernak, A. R.; Mustain, W. E.; Nijmeijer, K.; Scott, K.; Xu, T. W.; Zhuang, L. Energ. Environ. Sci. 2014, 7, 3135.

(4)  Couture, G.; Alaaeddine, A.; Boschet, F.; Ameduri, B. Prog. Polym. Sci. 2011, 36, 1521.

(5)  Merle, G.; Wessling, M.; Nijmeijer, K. J. Membr. Sci. 2011, 377, 1.

(6)  Varcoe, J. R.; Slade, R. C. T. Fuel Cells 2005, 5, 187.

(7)  John, J.; Hugar, K. M.; Rivera-Meléndez, J.; Kostalik, H. A.; Rus, E. D.; Wang, H.; Coates, G. W.; Abruña, H. D. J. Am. Chem. Soc. 2014, 136, 5309.

16:45 | Closing Words

17:40 | Sightseeing

Partners

Organising Committee

Dr. Alexander Dyck – DLR Institute of Networked Energy Systems (Germany)
Prof. Dirk Henkensmeier – Korea Institute of Science and Technology (KIST, South Korea)
Prof. Artur Michalak – Jagiellonian University in Krakow (Poland)

Registration

The participation fee of €380 is payable after receipt of invoice. For registration please complete the “Workshop Registration Form” and submit it by fax or email to DLR Institute of Networked Energy Systems by June 1st 2018.

Due to the limited number of participants, registrations are considered in order of receipt.

DLR Institute of Networked Energy Systems
Carl-von-Ossietzky-Str. 15 | 26129 Oldenburg | Germany
Phone: +49 441 99906-326
Fax: +49 441 99906-109
Email: emea-ve@dlr.de

Venue

The spa town Bad Zwischenahn is located in the north-west of Germany and is a famous recreational area because of its colorful flowering rhododendron shrubs and park-like landscape. The city can be reached conveniently by train or by car. Bremen Airport is located nearby.

The Workshop will be held at the conference and golfing hotel “Hansens Haus am Meer“, which is located directly in the spa gardens at the lake “Zwischenahner Meer”, the third largest lake in Lower Saxony.

EMEA2017_Venue_1
EMEA2017_Venue_2
EMEA2017_Venue_3

Accommodation

Bad Zwischenahn has a range of hotels in a variety of price categories. Rooms can also be booked at the conference hotel „Hansens Haus am Meer“.

If you are interested in booking a room in the conference hotel for your overnight stay in Bad Zwischenahn, you can do so by writing an email directly to the hotel (rezeption@hausammeer.de). Rooms are 98.00 € per night. Please refer to the workshop when booking.

Hansens Haus am Meer Hotel
Auf dem Hohen Ufer 25
26160 Bad Zwischenahn, Germany
Phone: +49 4403 940-0
Email: rezeption@hausammeer.de
www.hausammeer.de

Travel

By Plane:
The nearest international airport is Bremen, which is 60 km from Bad Zwischenahn.

By Train:
Bad Zwischenahn has a train station that is served by trains from the rail transport providers “Deutsche Bahn” (www.bahn.de) and “Regio-S-Bahn” (www.regiosbahn.de).

The “Hansens Haus am Meer” hotel offers a free shuttle service from the train station to the hotel on request.

By Car:
Coming from Bremen (A28):
Follow the A28 autobahn in the directions for Oldenburg / Emden / Leer. In Oldenburg, at the interchange “Oldenburg West“ continue to Emden / Leer on the A28. Leave the autobahn at the exit ramp No. 9 “Neuenkruge” and follow the road signposts to Bad Zwischenahn.

Coming from Leer / Netherlands (A31):
Change to the A31 autobahn at the “Leer” junction and follow the A28 in the direction for Oldenburg. Leave the autobahn at the exit ramp No. 8 “Zwischenahner Meer” and follow the road signs to Bad Zwischenahn.

Information

The conference fee of €380 includes the lab tour, lunch and coffee breaks on both days as well as the Get-together on Tuesday evening and the conference dinner on Wednesday evening and the VAT. Also covered is the bus tour to the DLR Institute of Networked Energy Systems.

DLR Institute of Networked Energy Systems may charge an administration fee of EUR 70.00 for any change or cancellation of registration. Cancellation must be received by DLR Institute of Networked Energy Systems in writing up until seven days prior to the event. Cancellations received after this date will be charged the full fee.

The program is subject to amendment. In the unlikely event of it being cancelled for reasons beyond the control of DLR Institute of Networked Energy Systems, registration fees already paid will be refunded.

If you have any further questions, please do not hesitate to contact us. Workshop contact: Jocelyne Hansen –phone: +49 441 99906-326 – e-mail: emea-ve@dlr.de