ABSTRACT
Optimal pH conditions for efficient artificial photosynthesis, hydrogen/oxygen evolution reactions, and photoreduction of carbon dioxide are now successfully achievable with catalytic bipolar membranes-integrated water dissociation and in-situ acid-base generations. However, inefficiency and instability are severe issues in state-of-the-art membranes, which need to urgently resolve with systematic membrane designs and innovative, inexpensive junctional catalysts. Here we show a shielding and in-situ formation strategy of fully-interconnected earth-abundant goethite Fe+3O(OH) catalyst, which lowers the activation energy barrier from 5.15 to 1.06 eV per HO - H bond and fabricates energy-efficient, cost-effective, and durable shielded catalytic bipolar membranes. Small water dissociation voltages at limiting current density (ULCD: 0.8 V) and 100 mA cm-2 (U100: 1.1 V), outstanding cyclic stability at 637 mA cm-2, long-time electro-stability, and fast acid-base generations (H2SO4: 3.9 ± 0.19 and NaOH: 4.4 ± 0.21 M m-2 min-1 at 100 mA cm-2) infer confident potential use of the novel bipolar membranes in emerging sustainable technologies.
ABSTRACT
Low theoretical capacities of the commercial cathode materials (olivine: â¼170 mA h g-1 and spinel: â¼140 mA h g-1) dictate the need for higher energy density alternates such as nickel-rich (denotes as NCM) materials with a theoretical capacity of â¼270 mA h g-1. However, low conductivity and the bulk degradation after direct contact with liquid electrolytes, especially at temperatures higher than 50 °C, are the biggest issues to resolve for safe use and confident commercialization of the NCM materials. In this context, we first report "La4NiLiO8 shields" to simultaneously boost charge conduction characteristics and circumvent the electrolytic degradation of NCM. Consequently, the La4NiLiO8-shielded LiNi0.5Co0.2Mn0.3O2 (LSN5) not only offers a 4.1× less charge transfer resistance and significantly higher discharge capacity (219.7 mA h g-1) than the nonshielded NCM (187 mA h g-1) and theoretical capacities of commercial cathode materials but also maintains more than 91.7% of capacity retention at 25 °C after 500 cycles and 84.2% at 60 °C after 200 cycles. In contrast, the nonshielded NCM cathodes can only provide 58.9 and 45.5% capacity retentions at corresponding test temperatures and performance cycles. The acquired excellent electrochemical performance and battery stability at both the ambient and high-temperature conductions infer great importance of the novel La4NiLiO8 shields in developing high-performance safe secondary batteries.
ABSTRACT
Artificial counterparts of conical-shaped transmembrane protein channels are of interest in biomedical sciences for biomolecule detection and selective ion permeation based on ionic size and/or charge differences. However, industrial-scale applications such as seawater desalination, separation of mono- from divalent cations, and treatment of highly-saline industrial waste effluents are still big challenges for such biomimetic channels. A simple monomer seeding experimental approach is used to grow ionically conductive biomimetic charged nanocone pores at the surface of an acid-functionalized membrane. These readily scalable nanocone membranes enable ultra-fast cation permeation (Na+ =8.4× vs. Mg2+ =1.4×) and high ion charge selectivity (Na+ /Mg2+ =6×) compared to the commercial state-of-the-art permselective membrane (CSO, Selemion, Japan) owing to negligible surface resistance and positively charged conical pore walls.
