Cation Vacancies Enable Anion Redox in Li Cathodes.

Conventional Li-ion battery intercalation cathodes leverage charge compensation that is formally associated with redox on the transition metal. Employing the anions in the charge compensation mechanism, so-called anion redox, can yield higher capacities beyond the traditional limitations of intercalation chemistry. Here, we aim to understand the structural considerations that enable anion oxidation and focus on processes that result in structural changes, such as the formation of persulfide bonds. Using a Li-rich metal sulfide as a model system, we present both first-principles simulations and experimental data that show that cation vacancies are required for anion oxidation. First-principles simulations show that the oxidation of sulfide to persulfide only occurs when a neighboring vacancy is present. To experimentally probe the role of vacancies in anion redox processes, we introduce vacancies into the Li2TiS3 phase while maintaining a high valency of Ti. When the cation sublattice is fully occupied and no vacancies can be formed through transition metal oxidation, the material is electrochemically inert. Upon introduction of vacancies, the material can support high degrees of anion redox, even in the absence of transition metal oxidation. The model system offers fundamental insights to deepen our understanding of structure-property relationships that govern reversible anion redox in sulfides and demonstrates that cation vacancies are required for anion oxidation, in which persulfides are formed.

CD-MOF-1 for CO2 Uptake: Remote and Hybrid Green Chemistry Synthesis of a Framework Material with Environmentally Conscious Applications.

The chemistry of metal-organic frameworks (MOFs) has the potential to introduce high school and undergraduate students to the fundamental chemical principles of structure and bonding, enhance the development of skills in synthesis and crystal growth, and promote hands-on experience with gas capture and host-guest chemistry of emerging materials with desirable environmental applications. However, most available experiments in the pedagogical literature involving MOFs require laboratory equipment and the use of hazardous chemicals to facilitate crystal growth and the study of structure-property relationships. To remedy this gap in the literature, this paper describes an adapted experimental approach designed specifically for a household environment or low-resource laboratory to grow, activate, and use cyclodextrin-based MOFs for CO2 uptake. This experiment implements a simple procedure that can be carried out safely without access to specialized equipment or laboratory infrastructure. Despite the simplicity of the experimental design, this experiment presents an intellectually engaging opportunity for high school and undergraduate students to explore crystal growth and nucleation, coordination chemistry, and host-guest chemistry as well as green chemistry concepts such as the choice of benign reagents and solvents, and applications of porous materials for gas uptake.

Bimetallic Two-Dimensional Metal-Organic Frameworks for the Chemiresistive Detection of Carbon Monoxide.

This paper describes the demonstration of a series of heterobimetallic, isoreticular 2D conductive metal-organic frameworks (MOFs) with metallophthalocyanine (MPc, M=Co and Ni) units interconnected by Cu nodes towards low-power chemiresistive sensing of ppm levels of carbon monoxide (CO). Devices achieve a sub-part-per-million (ppm) limit of detection (LOD) of 0.53 ppm toward CO at a low driving voltage of 0.1 V. MPc-based Cu-linked MOFs can continuously detect CO at 50 ppm, the permissible exposure limit required by the Occupational Safety and Health Administration (OSHA), for multiple exposures, and realize CO detection in air and in humid environment. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), density functional theory (DFT) calculations, and comparison experiments suggest the contribution of Cu nodes to CO binding and the essential role of MPc units in tuning and amplifying the sensing response.

Reducing Voltage Hysteresis in Li-Rich Sulfide Cathodes by Incorporation of Mn.

Conventional intercalation-based cathode materials in Li-ion batteries are based on charge compensation of the redox-active cation and can only intercalate one mole of electron per formula unit. Anion redox, which employs the anion sublattice to compensate charge, is a promising way to achieve multielectron cathode materials. Most anion redox materials still face the problems of slow kinetics and large voltage hysteresis. One potential solution to reduce voltage hysteresis is to increase the covalency of the metal-ligand bonds. By substituting Mn into the electrochemically inert Li1.33Ti0.67S2 (Li2TiS3), anion redox can be activated in the Li1.33-2y/3Ti0.67-y/3Mn y S2 (y = 0-0.5) series. Not only do we observe substantial anion redox, but the voltage hysteresis is significantly reduced, and the rate capability is dramatically enhanced. The y = 0.3 phase exhibits excellent rate and cycling performance, maintaining 90% of the C/10 capacity at 1C, which indicates fast kinetics for anion redox. X-ray absorption spectroscopy (XAS) shows that both the cation and anion redox processes contribute to the charge compensation. We attribute the drop in hysteresis and increase in rate performance to the increased covalency between the metal and the anion. Electrochemical signatures suggest the anion redox mechanism resembles holes on the anion, but the S K-edge XAS data confirm persulfide formation. The mechanism of anion redox shows that forming persulfides can be a low hysteresis, high rate capability mechanism enabled by the appropriate metal-ligand covalency. This work provides insights into how to design cathode materials with anion redox to achieve fast kinetics and low voltage hysteresis.