As opposed to the standard graphite anode used for lithium (Li) ion batteries (LIBs), a standard anode material for sodium (Na) ion batteries (NIBs) has not yet been reported. Black phosphorus is potentially very attractive as an anode material for NIBs, as it has a layered structure similar to graphite but a greater interlayer distance. In this work, we propose an atomistic mechanism for the sodiation of black phosphorus, based on first-principle calculations. The layered structure of black phosphorous is maintained up to the composition of Na 0.25 P, with one-dimensional sodiation (an intercalation process) occurring in the interlayer spaces of the black phosphorus, resulting in sliding of the phosphorene layers because one Na atom tends to bind to four P atoms. At Na levels beyond Na 0.25 P, the intercalation process changes to an alloying process. Sodiation exceeding the critical composition leads to breaking of P-P bonds and eventual formation of an amorphous phase from the layered Na x P structure. After the P-P bonds in the layered Na x P structure are broken, in a progress in which staggered P-P bonds are preferentially broken rather than planar P-P bonds, P 2 dumbbells are generated. As sodiation proceeds further, most of the P 2 dumbbells become isolated P atoms. Thus, in the amorphous Na 3 P phase, only low-coordinate P components such as isolated atoms (primarily) and dumbbells are found. We expect that our comprehensive understanding of the sodiation mechanism in black phosphorus will provide helpful guidelines in designing new types of black phosphorus anodes to obtain better performing NIBs.

The reaction mechanism of area-selective atomic layer deposition (AS-ALD) of AlO thin films using self-assembled monolayers (SAMs) was systematically investigated by theoretical and experimental studies. Trimethylaluminum (TMA) and HO were used as the precursor and oxidant, respectively, with octadecylphosphonic acid (ODPA) as an SAM to block AlO film formation. However, AlO layers began to form on the ODPA SAMs after several cycles, despite reports that CH-terminated SAMs cannot react with TMA. We showed that TMA does not react chemically with the SAM but is physically adsorbed, acting as a nucleation site for AlO film growth. Moreover, the amount of physisorbed TMA was affected by the partial pressure. By controlling it, we developed a new AS-ALD AlO process with high selectivity, which produces films of ∼60 nm thickness over 370 cycles. The successful deposition of AlO thin film patterns using this process is a breakthrough technique in the field of nanotechnology.

We propose the ReaxFF reactive force field as a simulation protocol for predicting the evolution of solid-electrolyte interphase (SEI) components such as gases (CH, CO, CO, CH, and CH), and inorganic (LiCO, LiO, and LiF) and organic (ROLi and ROCOLi: R = -CH or -CH) products that are generated by the chemical reactions between the anodes and liquid electrolytes. ReaxFF was developed from ab initio results, and a molecular dynamics simulation with ReaxFF realized the prediction of SEI formation under real experimental conditions and with a reasonable computational cost. We report the effects on SEI formation of different kinds of Si anodes (pristine Si and SiO), of the different types and compositions of various carbonate electrolytes, and of the additives. From the results, we expect that ReaxFF will be very useful for the development of novel electrolytes or additives and for further advances in Li-ion battery technology.

For the practical use of silicon nanowires (Si NWs) as anodes for Li-ion batteries, understanding their lithiation and delithiation mechanisms at the atomic level is of critical importance. Here, we report the mechanisms for the lithiation and delithiation of Si NWs determined using a large-scale molecular dynamics (MD) simulation with a reactive force field (ReaxFF). The ReaxFF is developed in this work using first-principles calculations. Our ReaxFF-MD simulation shows that an anisotropic volume expansion behavior of Si NWs during lithiation is dependent on the surface structures of the Si NWs; however, the volumes of the fully lithiated Si NWs are almost identical irrespective of the surface structures. During the lithiation process, Li atoms penetrate into the lattices of the crystalline Si (c-Si) NWs preferentially along the ⟨110⟩ or ⟨112⟩ direction, and then the c-Si changes into amorphous Li x Si (a-Li x Si) phases due to the simultaneous breaking of Si–Si bonds as a result of the tensile stresses between Si atoms. Before the complete amorphization of the Si NWs, we observe the formation of silicene-like structures in the NWs that are eventually broken into low-coordinated components, such as dumbbells and isolated atoms. However, during delithiation of the Li x Si NWs, we observe the formation of a small amount of c-Si nuclei in the a-Li x Si matrix below a composition of Li1.4Si ≈ Li1.5Si, in which the volume fraction of formed c-Si phases relies on the delithiation rate. We also demonstrate that the two-phase structure can be thermodynamically more favorable than the single-phase a-Li x Si. We expect that our comprehensive understanding of the lithiation and delithiation mechanisms along with the developed ReaxFF for Li–Si systems will provide helpful guidelines in designing Si anodes to obtain better performing Li-ion batteries.

The development of catalysts for the electrochemical N2 reduction reaction (NRR) with a low limiting potential and high Faradaic efficiency is highly desirable but remains challenging. Here, to achieve acceleration, we develop and report a slab graph convolutional neural network (SGCNN), an accurate and flexible machine learning (ML) model that is suited for probing surface reactions in catalysis. With a self-accumulated database of 3040 surface calculations at the density-functional-theory (DFT) level, SGCNN predicted the binding energies, ranging over 8 eV, of five key adsorbates (H, N2, N2H, NH, NH2) related to NRR performance with a mean absolute error (MAE) of only 0.23 eV. SGCNN only requires the low-level inputs of elemental properties available in the periodic table of elements and connectivity information of constituent atoms; thus, accelerations can be realized. Via a combined process of SGCNN-driven predictions and DFT verifications, four novel catalysts in the L12 crystal space, including V3Ir­(111), Tc3Hf­(111), V3Ni­(111), and Tc3Ta­(111), are proposed as stable candidates that likely exhibit both a lower limiting potential and higher Faradaic efficiency in the NRR, relative to the reference Mo(110). The ML work combined with a statistical data analysis reveals that catalytic surfaces with an average d-orbital occupation between 4 and 6 could lower the limiting potential and potentially overcome the scaling relation in the NRR.

Using first-principles calculations, we describe and compare atomistic lithiation, sodiation, and magnesiation processes in black phosphorous with a layered structure similar to graphite for Li-, Na-, and Mg-ion batteries because graphite is not considered to be an electrode material for Na- and Mg-ion batteries. The three processes are similar in that an intercalation mechanism occurs at low Li/Na/Mg concentrations, and then further insertion of Li/Na/Mg leads to a change from the intercalation mechanism to an alloying process. Li and Mg show a columnar intercalation mechanism and prefer to locate in different phosphorene layers, while Na shows a planar intercalation mechanism and preferentially localizes in the same layer. In addition, we compare the mechanical properties of black phosphorous during lithiation, sodiation, and magnesiation. Interestingly, lithiation and sodiation at high concentrations (Li2P and Na2P) lead to the softening of black phosphorous, whereas magnesiation shows a hardening phenomenon. In addition, the diffusion of Li/Na/Mg in black phosphorus during the intercalation process is an easy process along one-dimensional channels in black phosphorus with marginal energy barriers. The diffusion of Li has a lower energy barrier in black phosphorus than in graphite.

Tungsten–nitrogen (W–N) codoping has been known to enhance the photocatalytic activity of anatase TiO2 nanoparticles by utilizing visible light. The doping effects are, however, largely dependent on calcination or annealing conditions, and thus, the massive production of quality-controlled photocatalysts still remains a challenge. Using density functional theory (DFT) thermodynamics and time-dependent DFT computations (TDDFT), we investigate the atomic structures of N doping and W–N codoping in anatase TiO2, as well as the effect of the thermal processing conditions. We find that W and N dopants predominantly constitute two complex structures: an N interstitial site near a Ti vacancy in the triple charge state ((VTi-Ni)3–) and the simultaneous substitutions of Ti by W and the nearest O by N ((WTi-NO)+). The latter case induces highly localized shallow in-gap levels near the conduction band minimum (CBM) and the valence band maximum (VBM), whereas the (VTi-Ni)3– defect complex yielded deep levels (1.9 eV above the VBM). Electronic structures suggest that (WTi-NO)+ improves the photocatalytic activity of anatase by band gap narrowing, while (VTi-Ni)3– degrades the activity by an in-gap state-assisted electron–hole recombination, which explains the experimentally observed deep-level-related photon absorption. Through the real-time propagation of TDDFT, we demonstrate that the presence of (VTi-Ni)3– attracts excited electrons from the conduction band to a localized in-gap state within a much shorter time than the flat band lifetime of TiO2. On the basis of these results, we suggest that calcination under N-rich and O-poor conditions is desirable to eliminate the deep-level states caused by (VTi-Ni)3– and to improve photocatalysis.

We propose a recently discovered material, namely, β-CuGaO2 [T. Omata et al., J. Am. Chem. Soc. 2014, 136, 3378] as a strong candidate material for efficient ferroelectric photovoltaics (FPVs). According to first-principles predictions exploiting hybrid density functional, β-CuGaO2 is ferroelectric with a remarkably large remanent polarization of 83.80 μC/cm2, even exceeding that of the prototypic FPV material, BiFeO3. Quantitative theoretical analysis further indicates the asymmetric Ga 3d z 2 –O 2p z hybridization as the origin of the Pna21 ferroelectricity. In addition to the large displacive polarization, unusually small band gap (1.47 eV) and resultantly strong optical absorptions additionally differentiate β-CuGaO2 from conventional ferroelectrics; this material is expected to overcome critical limitations of currently available FPVs.