Justin M. Whiteley

Ionic Covalent Organic Frameworks with Spiroborate Linkage

A novel type of ionic covalent organic framework (ICOF), which contains sp(3)  hybridized boron anionic centers and tunable countercations, was constructed by formation of spiroborate linkages. These ICOFs exhibit high BET surface areas up to 1259 m(2)  g(-1) and adsorb a significant amount of H2 (up to 3.11 wt %, 77 K, 1 bar) and CH4 (up to 4.62 wt %, 273 K, 1 bar). Importantly, the materials show good thermal stabilities and excellent resistance to hydrolysis, remaining nearly intact when immersed in water or basic solution for two days. The presence of permanently immobilized ion centers in ICOFs enables the transportation of lithium ions with room-temperature lithium-ion conductivity of 3.05×10(-5)  S cm(-1) and an average Li(+) transference number value of 0.80±0.02. Our approach thus provides a convenient route to highly stable COFs with ionic linkages, which can potentially serve as absorbents for alternative energy sources such as H2, CH4, and also as solid lithium electrolytes/separators for the next-generation lithium batteries.

Ultra‐thin Solid‐State Li‐Ion Electrolyte Membrane Facilitated by a Self‐Healing Polymer Matrix

Thin solid membranes are formed by a new strategy, whereby an in situ derived self-healing polymer matrix that penetrates the void space of an inorganic solid is created. The concept is applied as a separator in an all-solid-state battery with an FeS2 -based cathode and achieves tremendous performance for over 200 cycles. Processing in dry conditions represents a paradigm shift for incorporating high active-material mass loadings into mixed-matrix membranes.

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All-Solid-State Sodium Batteries

All-solid-state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium-ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium-ion cathodes leads to a volatile cathode-electrolyte interface and undesirable cell performance. Here we report a high-capacity organic cathode, Na4 C6 O6 , that is chemically and electrochemically compatible with sulfide electrolytes. A bulk-type ASSSB shows high specific capacity (184 mAh g-1 ) and one of the highest specific energies (395 Wh kg-1 ) among intercalation compound-based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na4 C6 O6 functions as a capable anode material, enabling a symmetric all-organic ASSSB with Na4 C6 O6 as both cathode and anode materials.

All-solid-state disordered LiTiS2 pseudocapacitor

Pseudocapacitive materials offer an opportunity to bridge the energy storage gap between supercapacitor and battery technologies. Herein is chronicled the first report of pseudocapacitance in a system devoid of liquid electrolytes, using the cathode material LiTiS2. It is demonstrated that due to extreme crystallite reduction to less than 3 nm, additional charge storage is derived by reducing surface Ti3+ to Ti2+ at higher voltages and more reversibly than traditionally shown. Due to facile diffusion pathways in 3-fold coordinated lithium along the TiS2 surfaces, disordered LiTiS2 can be used as a singular cathode without conductive additives. The result is a system exhibiting nearly 300 mA h g−1 at a rate of C/2 for 1000 cycles. Whereas active materials in liquid cells typically have size limitations before irreversibilities appear, the high pseudocapacitance demonstrated in this report indicates that active materials used in the solid-state could benefit from size reduction. Hopefully, a new avenue of research stems from this work to investigate mixed conductor nano-domains for solid-state battery/capacitor hybrids. The prospect of a solid-state pseudocapacitor unlocks a series of new applications that offer long shelf life, high temperature capabilities, and enhanced safety.