Graphite fluoride (CF x ) cathodes coupled with lithium anodes yield one of the highest theoretical specific capacities (>860 mAh/g) among primary batteries. In practice, the observed discharge voltage (∼2.5 V) is significantly lower than thermodynamic limits (>4.5 V), the discharge rate is low, and so far Li/CF x has only been used in primary batteries. Understanding the discharge mechanism at atomic length scales will improve practical CF x energy density, rate capability, and rechargeability. So far, purely experimental techniques have not identified the correct discharge mechanism or explained the discharge voltage. We apply density functional theory calculations to demonstrate that a CF x -edge propagation discharge mechanism based on lithium insertion at the CF/C boundary in partially discharged CF x exhibits a voltage range of 2.5 to 2.9 Vdepending on whether solvent molecules are involved. The voltages and solvent dependence agree with our discharge and galvanostatic intermittent titration technique measurements. The predicted discharge kinetics are consistent with CF x operations. Finally, we predict some Li/CF x rechargeability under the application of high potentials, along a charging pathway different from that of discharge. Our work represents a general, quasi-kinetic framework to understand the discharge of conversion cathodes, circumventing the widely used phase diagram approach which most likely does not apply to Li/CF x because equilibrium conditions are not attained in this system.

Electrocatalytic synthesis of high value-added urea and ethanol from carbon dioxide (CO2) and nitric oxide (NO) via C−N and C−C coupling reactions is one of the most attractive approaches. Nevertheless,...

Electrocatalytic CO2 reduction (CO2RR) is a feasible and economical way to eliminate CO2 by converting it into useful products. However, this process is hampered by the lack of a highly...

The electrochemical carbon dioxide reduction reaction (CO2RR) has been extensively studied due to its potential to reduce the globally accelerating CO2 emission and produce value-added chemicals and fuels. Despite great efforts to optimize the catalyst activity and selectivity, the development of robust design criteria for screening the catalysts and understanding the role of water and potassium for CO2 activation poses a significant challenge. Herein, a rapid method for screening single-atom catalysts (SACs) possessing different coordination structures toward the CO2RR process to form CO, namely, a metal atom supported on nitrogen-doped carbon nanotubes (M@CNT, M@1N_CNT, M@2N_CNT, and M@3N_CNT), was established using large-scale density functional theory computations. Adopting the free energy of *CO2 and *OH as screening descriptors, Fe@CNT, Cu@1N_CNT, Pd@2N_CNT, and Ni@3N_CNT were found to exhibit high activity for CO in the gas phase with the overpotential values of 0.22, 0.11, 0.13, and 0.05 V, respectively. Water and potassium present on the surface of the active sites can accelerate the activation of CO2 relative to the gas phase. Ni@3N_CNT shows the highest activity and selectivity in the environment having four water and one potassium. Particularly, the least absolute shrinkage and selection operator regression study revealed that the CO2 adsorption is intrinsically governed by the number of electrons lost by the metal atom in the three N-doped systems, which can be correlated to the distance of the metal atom from the plane of the coordination atom in the M@CNT system. Besides, the study proposes equations for the calculation of the free energy of CO2 adsorption. The current work not only advances the exploration of highly active SACs for the heterogeneous electrocatalytic systems for CO2RR but also highlights the significance of water and potassium in the aqueous solution.