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Condens. Matter 2022, 7, 8 5 of 9 Figure 3. AFO structure after Li intercalation and the corresponding adsorption energy (zero-point energy corrected; ∆E) and open-circuit voltage with respect to Li cathode (∆V). The pink, blue, red, grey, and white spheres represent the Li, Fe, oxygen, carbon, and hydrogen atoms, respectively. Natural bond-orbital (NBO) analysis was performed at the PBE0/cc-pVDZ level to identify the most important interactions involved in Li intercalation. Accordingly, charge transfer from the lone-pair (LP) orbitals of oxalate oxygen atoms to the anti-LP (LP*) orbital of Li is the only significant driver of Li intercalation into PHFO and AFO with stabilization energy of over 0.10 eV. In the case of FOD, charge transfer from the LP orbital of a water molecule’s oxygen atom to the LP* orbital of Li is the most important contributor to the intercalation process. This highlights the role of Li hydration in the electrochemical reaction. 3.3. Electrochemical Potential To evaluate the anodic potential, both the Li adsorption energy (∆E) and the open- circuit voltage (OCV; ∆V) were calculated using [40,41]: ∆E = EFO/xLi − EFO − xELi (1) ∆V = −(EFO/xLi − EFO − xELi−bulk)/xne (2) where FO represents FOD, PHFO or AFO, and EFO is the energy of Li-free FO. EFO/xLi, ELi and ELi−bulk are the total energies of the Li0 or Li+ intercalated FO, Li0 atom or Li+ ion and bulk Li metal, respectively. x is the number of intercalated Li0 atoms or Li+ ions (=1), n is the highest oxidation state of the intercalated Li (=1) and e is electron charge. To obtain ELi−bulk, the cohesion energy of Li metal (Ecoh) and the energy of Li atom (ELi) were used as follows [42,43]. ∆Ecoh = ELi − ELi−bulk = 1.65eV (3) Based on the values reported in Figures 1 and S2–S4, the intercalation of Li into the three ferrous oxalate models is favorable, but the adsorption potency decreases with the increase of water content of ferrous oxalate. OCV increases with the increase of the hydration level. For anodes, lower the OCV, better the battery performance [44]. Therefore, AFO would be a better anode material compared to FOD, and PHFO would display an intermediate efficiency. This finding is in line with a recent study of the effect of crystal water on the anodic efficiency of FOD [45], which finds that water molecules inhibit the electrochemical activity of ferrous oxalate by creating structural deficiencies. Our NBO results and the FOD structural transformations shown in Figure S4, also show that the structural water molecules hydrate Li, cause structural deficiencies, and inhibit the anodic potential of ferrous oxalate. Moreover, our results of Table 1 and Figures S5 and S6, indicate that the presence of water has two roles: (1) it affects the charge distribution of ferrous oxalate–higher the water content, lower the positive charge localized on the Fe ions, and (2) it lowers the energy levels of the ferrous-oxalate molecular orbitals and decreases thePDF Image | Anodic Activity of Hydrated and Anhydrous Iron (II) Oxalate in Li-Ion Batteries
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