Advanced large-scale electrochemical energy storage requires cost-effective battery systems with high energy densities. Aprotic sodium-oxygen (Na-O2) batteries offer advantages, being comprised of low-cost elements and possessing much lower charge overpotential and higher reversibility compared to their lithium-oxygen battery cousins. Although such differences have been explained by solution-mediated superoxide transport, the underlying nature of this mechanism is not fully understood. Water has been suggested to solubilize superoxide via formation of hydroperoxyl (HO2), but direct evidence of these HO2 radical species in cells has proven elusive. Here, we use ESR spectroscopy at 210 K to identify and quantify soluble HO2 radicals in the electrolyte-cold-trapped in situ to prolong their lifetime-in a Na-O2 cell. These investigations are coupled to parallel SEM studies that image crystalline sodium superoxide (NaO2) on the carbon cathode. The superoxide radicals were spin-trapped via reaction with 5,5-dimethyl-pyrroline N-oxide at different electrochemical stages, allowing monitoring of their production and consumption during cycling. Our results conclusively demonstrate that transport of superoxide from cathode to electrolyte leads to the nucleation and growth of NaO2, which follows classical mechanisms based on the variation of superoxide content in the electrolyte and its correlation with the crystallization of cubic NaO2. The changes in superoxide content upon charge show that charge proceeds through the reverse solution process. Furthermore, we identify the carbon-centered/oxygen-centered alkyl radicals arising from attack of these solubilized HO2 species on the diglyme solvent. This is the first direct evidence of such species, which are likely responsible for electrolyte degradation.

We present the development of an optically detected magnetic resonance (ODMR) system, which enables us to perform the ODMR measurements of a single defect in solids at high frequencies and high magnetic fields. Using the high-frequency and high-field ODMR system, we demonstrate 115 GHz continuous-wave and pulsed ODMR measurements of a single nitrogen-vacancy (NV) center in a diamond crystal at the magnetic field of 4.2 Tesla as well as investigation of field dependence (0 − 8 Tesla) of the longitudinal relaxation time (T 1 ) of NV centers in nanodiamonds.

We demonstrate grafting of nitroxide radicals on the surface of nanodiamonds (NDs). The surface of NDs is functionalized by azide groups. Nitroxide radicals are covalently bonded using Cu(I)-catalyzed azide/alkyne-click chemistry approach. The reaction is confirmed by infrared spectroscopy. The grafting of nitroxides is also verified by studying the rotational correlational time using electron paramagnetic resonance (EPR) spectroscopy. EPR study estimates that a few hundreds (tens) of nitroxide radicals are grafted on the surface of NDs with 100 nm (25 nm) of the average diameter.

Quantum optimal control can play a crucial role to realize a set of universal quantum logic gates with error rates below the threshold required for fault-tolerance. Open-loop quantum optimal control relies on accurate modeling of the quantum system under control, and does not scale efficiently with system size. These problems can be avoided in closed-loop quantum optimal control, which utilizes feedback from the system to improve control fidelity. In this paper, two gradient-based closed-loop quantum optimal control algorithms, the hybrid quantum-classical approach (HQCA) described in [Phys. Rev. Lett. 118, 150503 (2017)] and the finite-difference (FD) method, are experimentally investigated and compared to the open-loop quantum optimal control utilizing the gradient ascent method. We employ a solid-state ensemble of coupled electron-nuclear spins serving as a two-qubit system. Specific single-qubit and two-qubit state preparation gates are optimized using the closed-loop and open-loop methods. The experimental results demonstrate the implemented closedloop quantum control outperforms the open-loop control in our system. Furthermore, simulations reveal that HQCA is more robust than the FD method to gradient noise which originates from measurement noise in this experimental setting. On the other hand, the FD method is more robust to control field distortions coming from non-ideal hardware.