Improving Li-ion battery charge rate acceptance through highly ordered hierarchical electrode design

In Li-ion technology, increasing electrode loading (thickness) is one approach to improve performance; however, this approach typically compromises power density and safety. To achieve the goal of decoupling energy and power density, a novel electrode architecture is proposed. The electrode design enhances uniform ionic current, especially in thick electrodes. A highly ordered and hierarchical (HOH) graphite anode concept was designed, fabricated, and tested for efficacy. The HOH electrodes consisted of ordered arrays of macro-scale line-of-sight linear channels made through laser ablation. SEM and Raman spectroscopy demonstrated that laser ablation is a feasible approach to fabricate HOH electrodes without affecting the graphite anode chemistry, respectively. A 65–120% improvement in charge rate acceptance (5.5 mAh/cm²) was achieved in the HOH electrodes compared to conventional electrodes. A restricted diffusion direct current polarization test determined that the HOH design improved ionic flow throughout porous electrodes. Altogether, the results of this study suggest that improved charge rate acceptance can be achieved by engineering electrode porosity to mitigate the effects of concentration polarization in high energy density graphite anodes. These findings can facilitate the development of higher energy and power density Li-ion batteries, while improving resilience against Li plating under severe charge conditions.     

Enhancing sensitivity of quadrupolar nuclei in solid-state NMR with multiple rotor assisted population transfers

Rotor-assisted population transfer (RAPT) was developed as a method for enhancing MAS NMR sensitivity of quadrupolar nuclei by transferring polarization associated with satellite transitions to the central m=12-->-12 transition. After a single RAPT transfer, there still remains polarization in the satellite transitions that can be transferred to the central transition. This polarization is available without having to wait for the spin system to return to thermal equilibrium. We describe a new RAPT scheme that uses the remaining polarization of the satellites to obtain a further enhancement of the central transition by performing RAPT-enhanced experiments multiple times before waiting for re-equilibration of the spin system. For 27Al (I=5/2) in albite we obtain a multiple RAPT enhancement of 3.02, a 48% increase over single RAPT. For 93Nb (I=9/2) in NaNbO(3) we obtain a multiple RAPT enhancement of 5.76, an 89% increase over single RAPT. We also describe a data processing procedure for obtaining the maximum possible signal-to-noise ratio.     

Bilevel programming and the separation problem

In recent years, branch-and-cut algorithms have become firmly established as the most effective method for solving generic mixed integer linear programs (MILPs). Methods for automatically generating inequalities valid for the convex hull of solutions to such MILPs are a critical element of branch-and-cut. This paper examines the nature of the so-called separation problem, which is that of generating a valid inequality violated by a given real vector, usually arising as the solution to a relaxation of the original problem. We show that the problem of generating a maximally violated valid inequality often has a natural interpretation as a bilevel program. In some cases, this bilevel program can be easily reformulated as a simple single-level mathematical program, yielding a standard mathematical programming formulation for the separation problem. In other cases, no such polynomial-size single-level reformulation exists unless the polynomial hierarchy collapses to its first level (an event considered extremely unlikely in computational complexity theory). We illustrate our insights by considering the separation problem for two well-known classes of valid inequalities.