Long-Life Aqueous Zn-I2 Battery Enabled by a Low-Cost Multifunctional Zeolite Membrane Separator.

Aqueous zinc iodide (Zn-I2) batteries are promising large-scale energy-storage devices. However, the uncontrollable diffuse away/shuttle of soluble I3- leads to energy loss (low Coulombic efficiency, CE), and poor reversibility (self-discharge). Herein, we employ an ordered framework window within a zeolite molecular sieve to restrain I3- crossover and prepare zeolite molecular sieve particles into compact, large-scale, and flexible membranes at the engineering level. The as-prepared membrane can confine I3- within the catholyte region and restrain its irreversible escape, which is proved via space-resolution and electrochemical in situ time-resolution Raman technologies. As a result, overcharge/self-discharge and Zn corrosion are effectively controlled by zeolite separator. After replacing the typically used glass fiber separator to a zeolite membrane, the CE of Zn-I2 battery improves from 78.9 to 98.6% at 0.2 A/g. Besides, after aging at the fully charged state for 5.0 h, self-discharge is restrained and CE is enhanced from 44.0 to 85.65%. Moreover, the Zn-I2 cell maintains 91.0% capacity over 30,000 cycles at 4.0 A/g.

MCM-41/PVA Composite as a Separator for Zinc-Air Batteries.

Membrane separators are one of the critical components in zinc-air batteries (ZABs). In the control of mass transfer, and hence, electrochemical reaction, membrane separators have an important role to play. This work addresses the issue of battery performance in a ZAB via a new composite membrane separator based on polyvinyl alcohol (PVA). To enhance the electrolyte uptake and ionic conductivity, mesoporous Mobil Composition of Matter No. 41 (MCM-41) is incorporated as a filler in the membrane while maintaining its integrity. The presence of MCM-41 is seen to reduce the number of cycles of secondary ZABs due to the uninvited drawbacks of increased zincate crossover and reduced triple phase boundary at the air cathode, which is pivotal for oxygen reduction reaction. Overall, results suggest that the application of the MCM-41/PVA composite has the potential for use as a separator in high-capacity primary ZABs.

On the Maximum Obtainable Purity and Resultant Maximum Useful Membrane Selectivity of a Membrane Separator.

Design considerations concerning the maximum purity of a membrane separator, and the resultant maximum effective selectivity of the membranes were explored by modeling a binary gas membrane separator (pressure-driven permeance) using a dimensionless form. Although the maximum purity has an analytical solution at the limit of zero recovery or stage cut, this solution over-predicts the obtained purity as the recovery is increased. Furthermore, at combinations of high recovery, low feed mole fraction, and low pressure ratio, the maximum purity becomes independent of selectivity above some critical selectivity. As a consequence of this purity limitation, a maximum selectivity is defined at which further increases in selectivity will result in less than a 1% change in the final purity. An equation is obtained that specifies the region in which a limiting purity is less than unity (indicating the existence of a limiting selectivity); operating at less than the limiting pressure ratio results in a purity limitation less than unity. This regime becomes larger and more significant as the inlet mole fraction decreases (e.g., inlet feed mole fraction of 10% and pressure ratio of 100 results in a maximum useful membrane selectivity of only 130 at 95% recovery). These results suggest that membrane research should focus on increasing permeance rather than selectivity for low-concentration separations. The results found herein can be used to set benchmarks for membrane development in various gas separation applications.

Fabricating a Partially Fluorinated Hybrid Cation-Exchange Membrane for Long Durable Performance of Vanadium Redox Flow Batteries.

The long-term durability of vanadium redox flow batteries (VRFBs) depends on the stability and performance of the membrane separator. We have architected a hybrid membrane by uniform dispersion of MIL-101(Cr) (Cr-MOF) in a partially fluorinated polymer grafted with sulfonic acid groups (PHP@AMPSCr-MOF(1.0)). The single cell VRFB performance of the PHP@AMPSCr-MOF(1.0) membrane was studied in comparison with the Cr-MOF incorporated Nafion membrane (NafionCr-MOF(1.0)) and showed an excellent result with 97.5% Coulombic efficiency (CE) at 150 mA/cm2 without any significant deterioration in the charge-discharge process for 1500 cycles (over 650 h). Meanwhile, the CE value of the NafionCr-MOF membrane (94.5%) deteriorated after 800 cycles (about 360 h) under similar conditions. The high VRFB performance of the PHP@AMPSCr-MOF(1.0) membrane has been attributed to the synergized properties and good interactions between Cr-MOF and partially fluorinated polymer matrix responsible for the creation of hydrophilic proton-conducting channels to achieve high selectivity. Furthermore, the cost-effective polymer and thus membranes may open new windows for practical applications in other energy devices such as fuel cells, electrolysis, and water treatment.

Role of the Membrane Transport Mechanism in Electrochemical Nitrogen Reduction Experiments.

The electrochemical synthesis of ammonia through the nitrogen reduction reaction (NRR) is receiving much attention, since it is considered a promising alternative to the Haber-Bosch process. In NRR experiments, a Nafion membrane is generally adopted as a separator. However, its use is controversial since ammonia can be trapped in the membrane, to some extent, or even pass through it. We systematically investigate the interaction of a Nafion membrane with ammonia and with an electrolyte and compare it with Zirfon as a possible alternative separator. We show that Nafion containing ammonia can easily release it when immersed in a 0.1 M Na2SO4 ammonia-free electrolyte, due to the cation exchange mechanism (Na+-NH4+). Since Na2SO4 is a commonly adopted electrolyte for NRR experiments, this may cause serious measurement errors and non-reproducible results. The same experiments performed using the polysulfone Zirfon separator clearly show that it is immune to interactions with ammonia, because of its different ion conduction mechanism. The findings provide a deeper understanding of the choice of membrane and electrolyte to be adopted for NRR tests, and may allow one to obtain more accurate and reliable results.

Development and Application of Supported Ionic Liquid Membranes in Microbial Fuel Cell Technology: A Concise Overview.

Membrane separators are key elements of microbial fuel cells (MFCs), especially of those constructed in a dual-chamber configuration. Until now, membranes made of Nafion have been applied the most widely to set-up MFCs. However, there is a broader agreement in the literature that Nafion is expensive and in many cases, does not meet the actual (mainly mass transfer-specific) requirements demanded by the process and users. Driven by these issues, there has been notable progress in the development of alternative materials for membrane fabrication, among which those relying on the deployment of ionic liquids are emerging. In this review, the background of and recent advances in ionic liquid-containing separators, particularly supported ionic liquid membranes (SILMs), designed for MFC applications are addressed and evaluated. After an assessment of the basic criteria to be fulfilled by membranes in MFCs, experiences with SILMs will be outlined, along with important aspects of transport processes. Finally, a comparison with the literature is presented to elaborate on how MFCs installed with SILM perform relative to similar systems assembled with other, e.g., Nafion, membranes.