Effect of Membrane Properties on the Carbonation of Anion Exchange Membrane Fuel Cells.

Anion exchange membrane fuel cells (AEMFC) are potentially very low-cost replacements for proton exchange membrane fuel cells. However, AEMFCs suffer from one very serious drawback: significant performance loss when CO2 is present in the reacting oxidant gas (e.g., air) due to carbonation. Although the chemical mechanisms for how carbonation leads to voltage loss in operating AEMFCs are known, the way those mechanisms are affected by the properties of the anion exchange membrane (AEM) has not been elucidated. Therefore, this work studies AEMFC carbonation using numerous high-functioning AEMs from the literature and it was found that the ionic conductivity of the AEM plays the most critical role in the CO2-related voltage loss from carbonation, with the degree of AEM crystallinity playing a minor role. In short, higher conductivity-resulting either from a reduction in the membrane thickness or a change in the polymer chemistry-results in faster CO2 migration and emission from the anode side. Although this does lead to a lower overall degree of carbonation in the polymer, it also increases CO2-related voltage loss. Additionally, an operando neutron imaging cell is used to show that as AEMFCs become increasingly carbonated their water content is reduced, which further drives down cell performance.

Using operando techniques to understand and design high performance and stable alkaline membrane fuel cells.

There is a need to understand the water dynamics of alkaline membrane fuel cells under various operating conditions to create electrodes that enable high performance and stable, long-term operation. Here we show, via operando neutron imaging and operando micro X-ray computed tomography, visualizations of the spatial and temporal distribution of liquid water in operating cells. We provide direct evidence for liquid water accumulation at the anode, which causes severe ionomer swelling and performance loss, as well as cell dryout from undesirably low water content in the cathode. We observe that the operating conditions leading to the highest power density during polarization are not generally the conditions that allow for long-term stable operation. This observation leads to new catalyst layer designs and gas diffusion layers. This study reports alkaline membrane fuel cells that can be operated continuously for over 1000 h at 600 mA cm-2 with voltage decay rate of only 32-µV h-1 - the best-reported durability to date.

Rational Synthesis of Metallo-Cations Toward Redox- and Alkaline-Stable Metallo-Polyelectrolytes.

Cations are crucial components in emerging functional polyelectrolytes for a myriad of applications. Rapid development in this area necessitates the exploration of new cations with advanced properties. Herein we describe a combination of computational and experimental design of cobaltocene metallo-cations that have distinct electronic and redox properties. One of the direct outcomes on the first synthesis of a complete set of cation derivatives is to discover highly stable cations, which are further integrated to construct metallo-polyelectrolytes as anion-exchange membranes in solid-state alkaline fuel cells. The device performance of these polyelectrolytes under highly basic and oxidative environments is competitive with many organo-polyelectrolytes.

Poly(bis-arylimidazoliums) possessing high hydroxide ion exchange capacity and high alkaline stability.

Solid polymer electrolyte electrochemical energy conversion devices that operate under highly alkaline conditions afford faster reaction kinetics and the deployment of inexpensive electrocatalysts compared with their acidic counterparts. The hydroxide anion exchange polymer is a key component of any solid polymer electrolyte device that operates under alkaline conditions. However, durable hydroxide-conducting polymer electrolytes in highly caustic media have proved elusive, because polymers bearing cations are inherently unstable under highly caustic conditions. Here we report a systematic investigation of novel arylimidazolium and bis-arylimidazolium compounds that lead to the rationale design of robust, sterically protected poly(arylimidazolium) hydroxide anion exchange polymers that possess a combination of high ion-exchange capacity and exceptional stability.

Nitrogen-doped Carbon-CoOx Nanohybrids: A Precious Metal Free Cathode that Exceeds 1.0†W cm-2 Peak Power and 100†h Life in Anion-Exchange Membrane Fuel Cells.

Efficient and durable nonprecious metal electrocatalysts for the oxygen reduction (ORR) are highly desirable for several electrochemical devices, including anion exchange membrane fuel cells (AEMFCs). Here, a 2D planar electrocatalyst with CoOx embedded in nitrogen-doped graphitic carbon (N-C-CoOx ) was created through the direct pyrolysis of a metal-organic complex with a NaCl template. The N-C-CoOx catalyst showed high ORR activity, indicated by excellent half-wave (0.84 V vs. RHE) and onset (1.01 V vs. RHE) potentials. This high intrinsic activity was also observed in operating AEMFCs where the kinetic current was 100 mA cm-2 at 0.85 V. When paired with a radiation-grafted ETFE powder ionomer, the N-C-CoOx AEMFC cathode was able to achieve extremely high peak power density (1.05 W cm-2 ) and mass transport limited current (3 A cm-2 ) for a precious metal free electrode. The N-C-CoOx cathode also showed good stability over 100 hours of operation with a voltage decay of only 15 % at 600 mA cm-2 under H2 /air (CO2 -free) reacting gas feeds. The N-C-CoOx cathode catalyst was also paired with a very low loading PtRu/C anode catalyst, to create AEMFCs with a total PGM loading of only 0.10 mgPt-Ru cm-2 capable of achieving 7.4 W mg-1 PGM as well as supporting a current of 0.7 A cm-2 at 0.6 V with H2 /air (CO2 free)-creating a cell that was able to meet the 2019 U.S. Department of Energy initial performance target of 0.6 V at 0.6 A cm-2 under H2 /air with a PGM loading <0.125 mg cm-2 with AEMFCs for the first time.

The Effect of Ambient Carbon Dioxide on Anion-Exchange Membrane Fuel Cells.

Over the past 10 years, there has been a surge of interest in anion-exchange membrane fuel cells (AEMFCs) as a potentially lower cost alternative to proton-exchange membrane fuel cells (PEMFCs). Recent work has shown that AEMFCs achieve nearly identical performance to that of state-of-the-art PEMFCs; however, much of that data has been collected while feeding CO2 -free air or pure oxygen to the cathode. Usually, removing CO2 from the oxidant is done to avoid the detrimental effect of CO2 on AEMFC performance, through carbonation, whereby CO2 reacts with the OH- anions to form HCO3- and CO32- . In spite of the crucial importance of this topic for the future development and commercialization of AEMFCs, unfortunately there have been very few investigations devoted to this phenomenon and its effects. Much of the data available is widely spread out and there currently does not exist a resource that researchers in the field, or those looking to enter the field, can use as a reference text that explains the complex influence of CO2 and HCO3- /CO32- on all aspects of AEMFC performance. The purpose of this Review is to summarize the experimental and theoretical work reported to date on the effect of ambient CO2 on AEMFCs. This systematic Review aims to create a single comprehensive account of what is known regarding how CO2 behaves in AEMFCs, to date, as well as identify the most important areas for future work in this field.

Preferentially Oriented Ag Nanocrystals with Extremely High Activity and Faradaic Efficiency for CO2 Electrochemical Reduction to CO.

Selective electrochemical reduction of CO2 is one of the most important processes to study because of its promise to convert this greenhouse gas to value-added chemicals at low cost. In this work, a simple anodization treatment was devised that first oxidizes Ag to Ag2CO3, then uses rapid electrochemical reduction to create preferentially oriented nanoparticles (PONs) of metallic Ag (PON-Ag) with high surface area as well as high activity and very high selectivity for the reduction of CO2 to CO. The PON-Ag catalyst was dominated by (110) and (100) orientation, which allowed PON-Ag to achieve a CO Faradaic efficiency of 96.7% at an operating potential of -0.69 V vs RHE. This performance is not only significantly higher than that of polycrystalline Ag (60% at -0.87 V vs RHE) but also represents one of the best combinations of activity and selectivity achieved to date - all with a very simple, scalable approach to electrode fabrication.

Effect of cobalt alloying on the electrochemical performance of manganese oxide nanoparticles nucleated on multiwalled carbon nanotubes.

MnO is an electrically insulating material which limits its usefulness in lithium ion batteries. We demonstrate that the electrochemical performance of MnO can be greatly improved by using oxygen-functional groups created on the outer walls of multiwalled carbon nanotubes (MWCNTs) as nucleation sites for metal oxide nanoparticles. Based on the mass of the active material used in the preparation of electrodes, the composite conversion-reaction anode material Mn1-x Co x O/MWCNT with x = 0.2 exhibited the highest reversible specific capacity, 790 and 553 mAhg-1 at current densities of 40 and 1600 mAg-1, respectively. This is 3.1 times higher than that of MnO/MWCNT at a charge rate of 1600 mAg-1. Phase segregation in the [Formula: see text] nanoparticles was not observed for x ≤ 0.15. Capacity retention in x = 0, 0.2, and 1 electrodes showed that the corresponding specific capacities were stabilized at 478, 709 and 602 mAhg-1 respectively, after 55 cycles at a current density of 400 mAg-1. As both MnO and CoO exhibit similar theoretical capacities and MnO/MWCNT and CoO/MWCNT anodes both exhibit lower performance than Mn0.8Co0.2O/MWCNT, the improved performance of the [Formula: see text] alloy likely arises from beneficial synergistic interactions in the bimetallic system.

Highly Conductive In-SnO2/RGO Nano-Heterostructures with Improved Lithium-Ion Battery Performance.

The increasing demand of emerging technologies for high energy density electrochemical storage has led many researchers to look for alternative anode materials to graphite. The most promising conversion and alloying materials do not yet possess acceptable cycle life or rate capability. In this work, we use tin oxide, SnO2, as a representative anode material to explore the influence of graphene incorporation and In-doping to increase the electronic conductivity and concomitantly improve capacity retention and cycle life. It was found that the incorporation of In into SnO2 reduces the charge transfer resistance during cycling, prolonging life. It is also hypothesized that the increased conductivity allows the tin oxide conversion and alloying reactions to both be reversible, leading to very high capacity near 1200 mAh/g. Finally, the electrodes show excellent rate capability with a capacity of over 200 mAh/g at 10C.

High stability, high activity Pt/ITO oxygen reduction electrocatalysts.

Sn-doped indium oxide (ITO) nanoparticles (NPs) were conceived as a high stability noncarbon support for Pt NPs, and the activity and stability of Pt/ITO for the oxygen reduction reaction (ORR) were probed. Sn was employed as the In(2)O(3) dopant to exploit the strong interaction between Sn and Pt that was previously reported to enhance the activity of Pt on Pt/SnO(2), while concomitantly avoiding the intrinsic stability limitations of SnO(2) and leveraging the high stability of bulk In(2)O(3) at ORR relevant potentials. The mass activity of Pt was extremely high on Pt/ITO, 621 ± 31 mA/mg(Pt), which far exceeded the 2015 DOE goal for Pt mass activity of 440 mA/mg(Pt). The enhanced ORR activity was linked to the faceting of the Pt NPs, which overwhelmingly consisted of Pt (111) facets. The stability of Pt/ITO was also very impressive, with the electrochemically active area unchanged and the Pt half wave potential shifting only 4 mV over 1000 potential cycles to 1.4 V vs RHE, a very harsh condition for ORR electrocatalysts where state-of-the-art Pt/C electrocatalysts typically show very poor stability.