Heterochiral π-Stacking Dimerization of Helical Secondary Structures with Emerging Supramolecular Chirality.

A specific interface mode type was observed between helical secondary structures, in which a left-handed (M) helix binds specifically to a right-handed (P) helix along the helical axis, leading to the formation of discrete heterochiral helical dimers. Moreover, a concealed supramolecular chirality within the meso-supramolecular dimers was unexpectedly discovered by chiral induction, and was further underpinned by covalent meso-helix structures.

Solid-Adsorbed Polymer-Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non-Aqueous Li Batteries.

Polymers are known to adsorb spontaneously from liquid solutions in contact with high-energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in-depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. These findings point to a simple, versatile approach for extending the lifetime of batteries.

Stabilizing Zinc Electrodeposition in a Battery Anode by Controlling Crystal Growth.

Reversible electrodeposition of metals at liquid-solid interfaces is a requirement for long cycle life in rechargeable batteries that utilize metals as anodes. The process has been studied extensively from the perspective of the electrochemical transformations that impact reversibility, however, the fundamental challenges associated with maintaining morphological control when a intrinsically crystalline solid metal phase emerges from an electrolyte solution have been less studied, but provide important opportunities for progress. A crystal growth stabilization method to reshape the initial growth and orientation of crystalline metal electrodeposits is proposed here. The method takes advantage of polymer-salt complexes (PEG-Zn2+ -aX- ) (a = 1,2,3) formed spontaneously in aqueous electrolytes containing zinc (Zn2+ ) and halide (X- ) ions to regulate electro-crystallization of Zn. It is shown that when X = Iodine (I), the complexes facilitate electrodeposition of Zn in a hexagonal closest packed morphology with preferential orientation of the (002) plane parallel to the electrode surface. This facilitates exceptional morphological control of Zn electrodeposition at planar substrates and leads to high anode reversibility and unprecedented cycle life. Preliminary studies of the practical benefits of the approach are demonstrated in Zn-I2 full battery cells, designed in both coin cell and single-flow battery cell configurations.

Lithium Iron Phosphate Enhances the Performance of High-Areal-Capacity Sulfur Composite Cathodes.

Lithium iron phosphate (LiFePO4, "LFP") was investigated as an additive in the cathode of lithium-sulfur (Li-S) batteries. LFP addition boosted the sulfur utilization during Li-S cycling, achieving an initial capacity of 1465 mAh/gS and a long cycle life (>300 cycles). Polysulfide adsorption experiments showed that LFP attracted polysulfides, and thus, the presence of LFP should alleviate the shuttle effect, a common failure mode. Postmortem characterization found iron phosphides, iron phosphates, and LiF in the electrode, indicating that LFP underwent dynamic reconstruction during Li-S cycling. We suspect that the formation of these species played a role in the observed performance. From the processing standpoint, adding LFP improved slurry rheology, making the preparation of a high-loading electrode more consistent. Benefiting from the high sulfur utilization and the ability to prepare electrodes with high mass loading, the S-LFP hybrid cell showed an excellent areal capacity of 2.65 mAh/cm2 and could be stably cycled at 2 mAh/cm2 for 250 cycles. Our results demonstrated the LFP addition as a promising strategy for realizing Li-S batteries with high sulfur loading and areal capacity.

Designing interphases for practical aqueous zinc flow batteries with high power density and high areal capacity.

Aqueous zinc flow batteries (AZFBs) with high power density and high areal capacity are attractive, both in terms of cost and safety. A number of fundamental challenges associated with out-of-plane growth and undesirable side reactions on the anode side, as well as sluggish reaction kinetics and active material loss on the cathode side, limit practical deployment of these batteries. We investigated artificial interphases created using a simple electrospray methodology as a strategy for addressing each of these challenges. The effectiveness of the electrospray interphases in full cell zinc-iodine flow batteries was evaluated and reported; it is possible to simultaneously achieve high power density [115 milliwatts per square centimeter (mW/cm2)] and high areal capacity [25 milliampere hour per square centimeter (mA·hour/cm2)]. Last, we extended it to aqueous zinc-bromine and zinc-vanadium flow batteries of contemporary interest. It is again found that high power density (255 and 260 mW/cm2, respectively) and high areal capacity (20 mA·hour/cm2) can be simultaneously achieved in AZFBs.

A biomimetic hierarchical structure with a hydrophilic surface and a hydrophobic subsurface constructed from waterborne polyurethanes containing a self-assembling peptide extender.

Constructing a biomimetic hierarchical structure is of great benefit to achieve materials with expected high performance. In this work, a new Fmoc-diphenylalanine (Fmoc-FF) based peptide extender (PPE) is synthesized for preparing a series of waterborne polyurethanes (WPUs) to construct a hydrophilic surface and a hydrophobic subsurface. A pre-assembly structure of the WPU emulsion particle is achieved by the introduction of PPE. It possesses a compact core consisting of hydrophobic segments of Fmoc-FF with π-π stacking and a loose shell consisting of hydrophilic polyethylene glycol (PEG) segments. The self-assembled Fmoc-FF could also enhance the phase separation between soft segments and hard segments. During film formation by demulsification, the outer PEG segments easily migrate onto the surface and the hydrophobic compact cores aggregate into the subsurface. Such an architecture endows WPU films with simultaneous biocompatibility, antifouling ability, and water resistance under wet conditions. This work provides a new insight into the design of a polymer emulsion with a pre-assembled phase to construct the expected hierarchical structure of films or coatings for biomaterials and antifouling materials.