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As the search for new battery chemistries with higher capacities and more stable supply chains expands, requiring increasingly complex electrolytes with multiple solvents and anions, it is becoming clear that understanding and controlling the working cation solvation structure is key to enabling improved stability and reversibility. In this work, we discover an emergent solvation behavior in multivalent electrolytes containing multiple anions, where bis(trifluoromethane sulfonyl) imide (TFSI⁻) anions that are fully dissociated in isolation form contact ion pairs with Zn²⁺ when combined with more strongly coordinating halides. This coordination modifies the electrochemical response, activating additional redox species as the halide associationmore » strength weakens (i.e., Cl⁻ > Br⁻ > I⁻) and systematically lowering overpotentials for metal deposition. This work suggests a completely new framework for electrolyte design in which anion chemistry can be used to tune both the bulk speciation and the interfacial solvation structure, enabling profound changes to the electrochemical behavior of the system.« less

The feasible commercialization of alkaline, phosphoric acid and polymer electrolyte membrane fuel cells depends on the development of oxygen reduction reaction (ORR) electrocatalysts with improved activity, stability, and selectivity. The rational design of surfaces to ensure these improved ORR catalytic requirements relies on the so-called "descriptors" (e.g., the role of covalent and noncovalent interactions on platinum surface active sites for ORR). Here, we demonstrate that through the molecular adsorption of melamine onto the Pt(111) surface [Pt(111)-M_ad], the activity can be improved by a factor of 20 compared to bare Pt(111) for the ORR in a strongly adsorbing sulfuric acid solution.more » Additionally, the M_ad moieties act as "surface-blocking bodies," selectively hindering the adsorption of (bi)sulfate anions (well-known poisoning spectator of the Pt(111) active sites) while the ORR is unhindered. This modified surface is further demonstrated to exhibit improved chemical stability relative to Pt(111) patterned with cyanide species (CN_ad), previously shown by our group to have a similar ORR activity increase compared to bare Pt(111) in a sulfuric acid electrolyte, with Pt(111)-M_ad retaining a greater than ninefold higher ORR activity relative to bare Pt(111) after extensive potential cycling as compared to a greater than threefold higher activity retained on a CN_ad-covered Pt(111) surface. We suggest that the higher stability of the Pt(111)-M_ad interface stems from melamine's ability to form intermolecular hydrogen bonds, which effectively turns the melamine molecules into larger macromolecular entities with multiple anchoring sites and thus more difficult to remove.« less

Developing next-generation battery chemistries that move beyond traditional Li-ion systems is critical to enabling transformative advances in electrified transportation and grid-level energy storage. Here, we provide the first evidence for common descriptors for improved reversibility of metal plating/stripping in nonaqueous electrolytes for multivalent ion batteries. Focusing first on the specific role of chloride (Cl^–) in promoting electrochemical reversibility in multivalent systems, rotating disk (RDE) and ring-disk electrode (RRDE) investigations were performed utilizing a variety of divalent cations (Mg²⁺, Zn²⁺, and Cu²⁺) and the bis-(trifluoromethane sulfonyl) imide (TFSI^–) anion. By introducing varying concentrations of Cl^–, a cooperative effect is observed betweenmore » TFSI^– and Cl^– that yields the more reversible behavior of mixed electrolytes relative to electrolytes containing only TFSI^–. This effect is shown to be general for Mg, Zn, and Cu electrodeposition, and mechanistic understanding of the role of Cl^– in improving reversibility of TFSI-based electrolytes is obtained through the combination of R(R)DE experimental results and density functional theory (DFT) evaluation of the redox activity and thermodynamic stability of various TFSI- and Cl-based solution complexes of metal ions. The cooperative anion effect is further generalized to other mixed-anion systems, where systematic variations in anion association strength predicted from DFT (i.e., Cl^– > OTf^– ≈ TFSI^– > BF₄^– > PF₆^–) yield corresponding trends in redox potentials and improvements of ≥200 mV in the reversibility of metal deposition/dissolution. These results identify anion association strength as a common descriptor for the reversibility of divalent metal anodes and suggest a set of general design principles for developing new electrolytes with improved activity and stability.« less

By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electroreduction reactions of HF, water and methanesulfonic acid on the single crystal (111) facets of Au, Pt, Ir and Cu in a variety of aprotic electrolytes.

The future of high-voltage rechargeable batteries is closely tied to the fundamental understanding of the processes that lead to the potential-dependent degradation of electrode materials and organic electrolytes. To date, however, there have been no methods able to provide quantitative, in situ and in real time information about the electrode dissolution kinetics and concomitant electrolyte decomposition during charge/discharge. We describe the development of such a method, which is of both fundamental and technological significance. Our novel approach enables simultaneous and independent measurements of transition-metal cation dissolution rates from different oxide hosts (Co^3+/4+ or Cr^3+/4+), deintercalation kinetics of working cations (Mg²⁺),more » and the relative rate of electrolyte decomposition.« less

The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. In this paper, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H₂. Although the kinetics of HF dissociation and the concomitant production of LiF and H₂ is dependent on the structure and nature of surface atoms, the underlying electrochemistrymore » is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Finally, our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.« less

Here, we developed a method for production of arrays of platinum nanocrystals of controlled size and shape using templates from ordered silica bead monolayers. Silica beads with nominal sizes of 150 and 450 nm were self-assembl into monolayers over strontium titanate single crystal substrates. The monolayers were used as shadow masks for platinum metal deposition on the substrate using the three-step evaporation technique. Produced arrays of epitaxial platinum islands were transformed into nanocrystals by annealing in a quartz tube in nitrogen flow. The shape of particles is determined by the substrate crystallography, while the size of the particles and theirmore » spacing are controlled by the size of the silica beads in the mono- layer mask. As a proof of concept, arrays of platinum nanocrystals of cubooctahedral shape were prepared on (100) strontium titanate substrates. We also characterized the nanocrystal arrays by atomic force microscopy, scanning electron microscopy, and synchrotron X-ray diffraction techniques.« less