The generation of renewable electricity is variable, leading to periodic oversupply. Excess power can be converted to H2via water electrolysis, but the conversion cost is currently too high. One way to decrease the cost of electrolysis is to increase the maximum productivity of electrolyzers. This study investigates how nano‐ and microstructured porous electrodes can improve the productivity of H2generation in a zero‐gap, flow‐through alkaline water electrolyzer. Three nickel electrodes—foam, microfiber felt, and nanowire felt—are studied to examine the tradeoff between surface area and pore structure on the performance of alkaline electrolyzers. Although the nanowire felt with the highest surface area initially provides the highest performance, this performance quickly decreases as gas bubbles are trapped within the electrode. The open structure of the foam facilitates bubble removal, but its small surface area limits its maximum performance. The microfiber felt exhibits the best performance because it balances high surface area with the ability to remove bubbles. The microfiber felt maintains a maximum current density of 25 000 mA cm−2over 100 h without degradation, which corresponds to a hydrogen production rate 12.5‐ and 50‐times greater than conventional proton‐exchange membrane and alkaline electrolyzers, respectively.
Using reverse osmosis membranes to control ion transport during water electrolysis
The decreasing cost of electricity produced using solar and wind and the need to avoid CO 2 emissions from fossil fuels has heightened interest in hydrogen gas production by water electrolysis. Offshore and coastal hydrogen gas production using seawater and renewable electricity is of particular interest, but it is currently economically infeasible due to the high costs of ion exchange membranes and the need to desalinate seawater in existing electrolyzer designs. A new approach is described here that uses relatively inexpensive commercially available membranes developed for reverse osmosis (RO) to selectively transport favorable ions. In an applied electric field, RO membranes have a substantial capacity for proton and hydroxide transport through the active layer while excluding salt anions and cations. A perchlorate salt was used to provide an inert and contained anolyte, with charge balanced by proton and hydroxide ion flow across the RO membrane. Synthetic seawater (NaCl) was used as the catholyte, where it provided continuous hydrogen gas evolution. The RO membrane resistance was 21.7 ± 3.5 Ω cm 2 in 1 M NaCl and the voltages needed to split water in a model electrolysis cell at current densities of 10–40 mA cm −2 were comparable to those found when using two commonly used, more expensive ion exchange membranes.
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- Award ID(s):
- 2027552
- NSF-PAR ID:
- 10249770
- Date Published:
- Journal Name:
- Energy & Environmental Science
- Volume:
- 13
- Issue:
- 9
- ISSN:
- 1754-5692
- Page Range / eLocation ID:
- 3138 to 3148
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
Polyamide reverse osmosis (PA-RO) membranes achieve remarkably high water permeability and salt rejection, making them a key technology for addressing water shortages through processes including seawater desalination and wastewater reuse. However, current state-of-the-art membranes suffer from challenges related to inadequate selectivity, fouling, and a poor ability of existing models to predict performance. In this Perspective, we assert that a molecular understanding of the mechanisms that govern selectivity and transport of PA-RO and other polymer membranes is crucial to both guide future membrane development efforts and improve the predictive capability of transport models. We summarize the current understanding of ion, water, and polymer interactions in PA-RO membranes, drawing insights from nanofiltration and ion exchange membranes. Building on this knowledge, we explore how these interactions impact the transport properties of membranes, highlighting assumptions of transport models that warrant further investigation to improve predictive capabilities and elucidate underlying transport mechanisms. We then underscore recent advances in in situ characterization techniques that allow for direct measurements of previously difficult-to-obtain information on hydrated polymer membrane properties, hydrated ion properties, and ion–water–membrane interactions as well as powerful computational and electrochemical methods that facilitate systematic studies of transport phenomena.more » « less
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null (Ed.)Seawater electrolysis is an attractive approach for producing clean hydrogen fuel in scenarios where freshwater is scarce and renewable electricity is abundant. However, chloride ions (Cl−) in seawater can accelerate electrode corrosion and participate in the undesirable chlorine evolution reaction (CER). This problem is especially acute in acidic conditions that naturally arise at the anode as a result of the desired oxygen evolution reaction (OER). Herein, we demonstrate that ultrathin silicon oxide (SiOx) overlayers on model platinum anodes are highly effective at suppressing the CER in the presence of 0.6 M Cl− in both acidic and unbuffered pH-neutral electrolytes by blocking the transport of Cl− to the catalytically active buried interface while allowing the desired oxygen evolution reaction (OER) to occur there. The permeability of Cl− in SiOx overlayers is 3 orders of magnitude less than that of Cl− in a conventional salt-selective membrane used in reverse osmosis desalination. The overlayers also exhibit robust stability over 12 h in chronoamperometry tests at moderate overpotentials. SiOx overlayers demonstrate a promising step toward achieving selective and stable seawater electrolysis without the need to adjust the pH of the electrolyte.more » « less
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Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of
trans -cyclooctenes. Atrans -cyclooctene–fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80 °C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by1H NMR spectroscopy when the polymers were treated with 2 M KOH in CD3OH at 80 °C for 30 d.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0ee02173c
