New Emerging Fast Charging Microscale Electrode Materials.

Fast charging lithium (Li)-ion batteries are intensively pursued for next-generation energy storage devices, whose electrochemical performance is largely determined by their constituent electrode materials. While nanosizing of electrode materials enhances high-rate capability in academic research, it presents practical limitations like volumetric packing density and high synthetic cost. As an alternative to nanosizing, microscale electrode materials cannot only effectively overcome the limitations of the nanosizing strategy but also satisfy the requirement of fast-charging batteries. Therefore, this review summarizes the new emerging microscale electrode materials for fast charging from the commercialization perspective. First, the fundamental theory of electronic/ionic motion in both individual active particles and the whole electrode is proposed. Then, based on these theories, the corresponding optimization strategies are summarized toward fast-charging microscale electrode materials. In addition, advanced functional design to tackle the mechanical degradation problems related to next generation high capacity alloy- and conversion-type electrode materials (Li, S, Si et al.) for achieving fast charging and stable cycling batteries. Finally, general conclusions and the future perspective on the potential research directions of microscale electrode materials are proposed. It is anticipated that this review will provide the basic guidelines for both fundamental research and practical applications of fast-charging batteries.

Emulating "Curvature-Enhanced Adsorbate Coverage" for Superconformal and Orientated Zn Electrodeposition in Zinc-ion-Batteries.

Uneven Zn deposition and unfavorable side reactions have prevented the reversibility of the Zn anode. Herein, we design a rearranged (002) textured Zn anode inspired by a traditional curvature-enhanced adsorbate coverage (CEAC) process to realize the highly reversible Zn anode. The rearranged (002) textured structure orientates the superconformal Zn deposition owing to the spatial deposition rate of the rearranged crystal planes, promoting bottom-up "superfilling" of the 3D Zn skeletons. Meanwhile, our designed anode also induces the epitaxial Zn deposition, alleviating the parasitic reactions owing to the lowest surface energy of the (002) plane. Attributed to these superiorities, uniform and oriented Zn deposition can be obtained, exhibiting an ultra-long lifespan over 479 hrs at an ultrahigh depth of discharge (DOD) of 82.12%. The Zn|Na2V6O16·3H2O battery delivers an improved cycling performance, even at a high area capacity of 5.15 mAh/cm2 with a low negative/positive (N/P) capacity ratio of 1.63. The superconformal deposition approach for Zn anodes paves the way for the practical application of high-performance zinc-ion batteries.

Understanding Doping of Quantum Materials.

Doping mobile carriers into ordinary semiconductors such as Si, GaAs, and ZnO was the enabling step in the electronic and optoelectronic revolutions. The recent emergence of a class of "quantum materials", where uniquely quantum interactions between the components produce specific behaviors such as topological insulation, unusual magnetism, superconductivity, spin-orbit-induced and magnetically induced spin splitting, polaron formation, and transparency of electrical conductors, pointed attention to a range of doping-related phenomena associated with chemical classes that differ from the traditional semiconductors. These include wide-gap oxides, compounds containing open-shell d electrons, and compounds made of heavy elements yet having significant band gaps. The atomistic electronic structure theory of doping that has been developed over the past two decades in the subfield of semiconductor physics has recently been extended and applied to quantum materials. The present review focuses on explaining the main concepts needed for a basic understanding of the doping phenomenology and indeed peculiarities in quantum materials from the perspective of condensed matter theory, with the hope of forging bridges to the chemists that have enabled the synthesis of some of the most interesting compounds in this field.

Effect of pressure on the electronic structure of antiferromagnetic and paramagnetic YNiO3: the role of disproportionation.

The dependence of electronic properties of quantum materials on external controls (e.g., pressure and temperature) is one of the fundamentals of neuromorphic computing, sensors, etc. Until recently, it has been believed that the theoretical description of such compounds cannot be accomplished using "traditional" density functional theory, and more advanced methods like dynamic mean-field theory should be utilized instead. Focusing here on the example of long-range ordered antiferromagnetic and paramagnetic YNiO3 phases, we show the interplay between spin and structural motifs under pressure and their impact on electronic properties. We successfully describe the insulating nature of both YNiO3 phases and the role of symmetry-breaking motifs in the band gap opening. Moreover, by analyzing the pressure-dependent distribution of local motifs, we show that external pressure can significantly reduce the band gap energy of both phases, originating from the reduction of structural and magnetic disproportionation - change in the distribution of local motifs. These results thus demonstrate that some of the experimental observations in quantum materials (e.g., YNiO3 compounds) can be fully understood without accounting for dynamic correlation.

Spontaneous off-stoichiometry as the knob to control the dielectric properties of gapped metals.

Using first-principles calculations and La3Te4 as an example of an n-type gapped metal, we demonstrate that gapped metals can develop spontaneous defect formation resulting in off-stoichiometric compounds. Importantly, these compounds have different free carrier concentrations and can be realized by optimizing the synthesis conditions. The ability to tune the free carrier concentration allows the tailoring of the intraband and interband transitions, thus controlling the optoelectronic properties of materials in general. Specifically, by realizing different off-stoichiometric La3-xTe4 compounds, it is possible to reach specific crossings of the real part of the dielectric function with the zero line, reduce the plasma frequency contribution to the absorption spectra, or, more generally, induce metal-to-insulator transition. This is particularly important in the context of optoelectronic, plasmonic, and epsilon-near-zero materials, as it enables materials design with a target functionality. While this work is limited to the specific gapped metal, we demonstrate that the fundamental physics is transferable to other gapped metals and can be generally used to design a wide class of new optoelectronic/plasmonic materials.

Mechanically Reinforced Localized Structure Design to Stabilize Solid-Electrolyte Interface of the Composited Electrode of Si Nanoparticles and TiO2 Nanotubes.

Silicon anode with extremely high theoretical specific capacity (≈4200 mAh g-1 ), experiences huge volume changes during Li-ion insertion and extraction, causing mechanical fracture of Si particles and the growth of a solid-electrolyte interface (SEI), which results in a rapid capacity fading of Si electrodes. Herein, a mechanically reinforced localized structure is designed for carbon-coated Si nanoparticles (C@Si) via elongated TiO2 nanotubes networks toward stabilizing Si electrode via alleviating mechanical strain and stabilizing the SEI layer. Benefited from the rational localized structure design, the carbon-coated Si nanoparticles/TiO2 nanotubes composited electrode (C@Si/TiNT) exhibits an ideal electrode thickness swelling, which is lower than 1% after the first cycle and increases to about 6.6% even after 1600 cycles. While for traditional C@Si/carbon nanotube composited electrode, the initial swelling ratio is about 16.7% and reaches ≈190% after 1600 cycles. As a result, the C@Si/TiNT electrode exhibits an outstanding capacity of 1510 mAh g-1 at 0.1 A g-1 with high rate capability and long-time cycling performance with 95% capacity retention after 1600 cycles. The rational design on mechanically reinforced localized structure for silicon electrode will provide a versatile platform to solve the current bottlenecks for other alloyed-type electrode materials with large volume expansion toward practical applications.

Elementary models of the "flux driven anti-ripening" during nanobelt growth.

A stirring solution hydrothermal approach is widely used to rationally grow elongated oxide nanostructures with controllable aspect ratios. Depending on the synthesis conditions, the following are observed: (i) no nanostructure formation (the system exists as a pure liquid), (ii) formation of nanostructure starting from a critical powder/initial volume of the liquid solution, and (iii) monotonic increase in the nanostructure's aspect ratio (towards asymptotic value) with stirring rate. Despite these experimental observations, the theoretical understanding of the process is limited. Herein, using an athermal ballistic atomic jump model, we develop a phenomenological theory of nanostructure growth under different stirring rates, demonstrating the conditions necessary for breaking the equilibrium Wulff shape, the formation of elongated one-dimensional structures, and explaining regimes (i-iii) reported experimentally. Moreover, the comparison of the phenomenological models without and with the account of ripening effects in the open ensemble of nanowires under stirring provides the theoretical guidance for the controllable growth of elongated nanostructures by the stirring solution hydrothermal approach.

Distance-Dependent Sign Reversal in the Casimir-Lifshitz Torque.

The Casimir-Lifshitz torque between two biaxially polarizable anisotropic planar slabs is shown to exhibit a nontrivial sign reversal in its rotational sense. The critical distance a_{c} between the slabs that marks this reversal is characterized by the frequency ω_{c}∼c/2a_{c} at which the in-planar polarizabilities along the two principal axes are equal. The two materials seek to align their principal axes of polarizabilities in one direction below a_{c}, while above a_{c} their axes try to align rotated perpendicular relative to their previous minimum energy orientation. The sign reversal disappears in the nonretarded limit. Our perturbative result, derived for the case when the differences in the relative polarizabilities are small, matches excellently with the exact theory for uniaxial materials. We illustrate our results for black phosphorus and phosphorene.

Suppression of surfaces states at cubic perovskite (001) surfaces by CO2 adsorption.

By using first-principles approach, the interaction of CO2 with (001) surfaces of six cubic ABO3 perovskites (A = Ba, Sr and B = Ti, Zr, Hf) is studied in detail. We show that CO2 adsorption results in the formation of highly stable CO3-like complexes with similar geometries for all investigated compounds. This reaction leads to the suppression of the surfaces states, opening the band gaps of the slab systems up to the corresponding bulk energy limits. For most AO-terminated ABO3(001) perovskite surfaces, a CO2 coverage of 0.25 was found to be sufficient to fully suppress the surface states, whereas the same effect can only be achieved at 0.50 CO2 coverage for the BO2-terminated surfaces. The largest band gap modulation among the AO-terminated surfaces was found for SrHfO3(001) and BaHfO3(001), whereas the most profound effect among the BO2-terminated surfaces was identified for SrTiO3(001) and BaTiO3(001). Based on these results and considering practical difficulties associated with measuring conductivity of highly resistive materials, TiO2-terminated SrTiO3(001) and BaTiO3(001) were identified as the most prospective candidates for chemiresistive CO2 sensing applications.

Tailoring electronic properties of multilayer phosphorene by siliconization.

Controlling the thickness dependence of electronic properties for two-dimensional (2d) materials is among the primary goals for their large-scale applications. Herein, employing a first-principles computational approach, we predict that Si interaction with multilayer phosphorene (2d-P) can result in the formation of highly stable 2d-SiP and 2d-SiP2 compounds with a weak interlayer interaction. Our analysis demonstrates that these systems are semiconductors with band gap energies that can be governed by varying the thicknesses and stacking arrangements. Specifically, the siliconization of phosphorene allows designing 2d-SiPx materials with a significantly weaker thickness dependence of electronic properties than that in 2d-P and to develop ways for their tailoring. We also reveal the spatial dependence of electronic properties for 2d-SiPx highlighting the difference in the effective band gaps for different layers. Particularly, our results show that the central layers in the multilayer 2d systems determine their overall electronic properties, while the role of the outermost layers is noticeably smaller.

Band gap modulation of SrTiO3 upon CO2 adsorption.

Herein, CO2 chemisorption on SrTiO3(001) surfaces is studied using ab initio calculations to establish new chemical sensing mechanisms. It was found that CO2 adsorption opens the band gap of the material. However, the mechanisms are different: the CO2 adsorption on the TiO2-terminated surface neutralizes the surface states at the valence band (VB) maximum, whereas for the SrO-terminated surface it suppresses the conduction band (CB) minimum. For the TiO2-terminated surface, the effect is explained by the passivation of dangling bonds, whereas for the SrO-terminated surface, the suppression is caused by surface relaxation. Modulation of the VB states implies a more direct change in charge distribution, and thus, the induced change in the band gap is more prominent at the TiO2 termination. Further, it has been shown that both CO2 adsorption energy and surface band gap are strongly dependent on CO2 coverage, suggesting that the observed effect can be utilized in sensing applications for a wide range of CO2 concentrations.

Reducing the Charge Carrier Transport Barrier in Functionally Layer-Graded Electrodes.

Lithium-ion batteries (LIBs) are primary energy storage devices to power consumer electronics and electric vehicles, but their capacity is dramatically decreased at ultrahigh charging/discharging rates. This mainly originates from a high Li-ion/electron transport barrier within a traditional electrode, resulting in reaction polarization issues. To address this limitation, a functionally layer-graded electrode was designed and fabricated to decrease the charge carrier transport barrier within the electrode. As a proof-of-concept, functionally layer-graded electrodes composing of TiO2 (B) and reduced graphene oxide (RGO) exhibit a remarkable capacity of 128 mAh g-1 at a high charging/discharging rate of 20 C (6.7 A g-1 ), which is much higher than that of a traditionally homogeneous electrode (74 mAh g-1 ) with the same composition. This is evidenced by the improvement of effective Li ion diffusivity as well as electronic conductivity in the functionally layer-graded electrodes.

Volume dependence of the dielectric properties of amorphous SiO2.

Using first principles calculations, the analysis of the dielectric properties of amorphous SiO2 (am-SiO2) was performed. We found that the am-SiO2 properties are volume dependent, and the dependence is mainly induced by the variation of nanoporosity at the atomic scale. In particular, both ionic and electronic contributions to the static dielectric constants are functions of volume with clear trends. Moreover, using the unique parameterization of the dielectric function provided in this work, we predict dielectric functions at imaginary frequencies of different SiO2 polymorphs having similar band gap energies.

Adsorption of metal adatoms on single-layer phosphorene.

Single- or few-layer phosphorene is a novel two-dimensional direct-bandgap nanomaterial. Based on first-principles calculations, we present a systematic study on the binding energy, geometry, magnetic moment and electronic structure of 20 different adatoms adsorbed on phosphorene. The adatoms cover a wide range of valences, including s and p valence metals, 3d transition metals, noble metals, semiconductors, hydrogen and oxygen. We find that adsorbed adatoms produce a rich diversity of structural, electronic and magnetic properties. Our work demonstrates that phosphorene forms strong bonds with all studied adatoms while still preserving its structural integrity. The adsorption energies of adatoms on phosphorene are more than twice higher than on graphene, while the largest distortions of phosphorene are only ∼0.1-0.2 Å. The charge carrier type in phosphorene can be widely tuned by adatom adsorption. The unique combination of high reactivity with good structural stability is very promising for potential applications of phosphorene.

A first principles study of CO2 adsorption on α-SiO2(001) surfaces.

In this work, using first principles calculations, an analysis of CO2 interaction with cleaved and reconstructed α-SiO2(001) surfaces was performed. We showed that CO2 could strongly interact with a cleaved surface forming CO3-like configurations. Here, the binding energy per CO2 molecule depends strongly on CO2 surface coverage and can reach -2.35 eV. Despite this, even with CO2 molecules, the cleaved surface has a substantially higher surface energy than that of the reoptimized "dense" surface. This observation is also consistent with molecular dynamics simulations. Because of this, for thermodynamically stable system, the interaction of CO2 molecules with a α-SiO2(001) surface should be treated as the physisorption of CO2 molecules on the reoptimized "dense" surface with the binding energy varying from -0.26 eV for single CO2 molecule adsorption to -0.32 eV per molecule for monolayer coverage.

Phosphorene as an anode material for Na-ion batteries: a first-principles study.

We systematically investigate a novel two-dimensional nanomaterial, phosphorene, as an anode for Na-ion batteries. Using first-principles calculations, we determine the Na adsorption energy, specific capacity and Na diffusion barriers on monolayer phosphorene. We examine the main trends in the electronic structure and mechanical properties as a function of Na concentration. We find a favorable Na-phosphorene interaction with a high theoretical Na storage capacity. We find that Na-phosphorene undergoes semiconductor-metal transition at high Na concentration. Our results show that Na diffusion on phosphorene is fast and anisotropic with an energy barrier of only 0.04 eV. Owing to its high capacity, good stability, excellent electrical conductivity and high Na mobility, monolayer phosphorene is a very promising anode material for Na-ion batteries. The calculated performance in terms of specific capacity and diffusion barriers is compared to other layered 2D electrode materials, such as graphene, MoS2, and polysilane.

Controlling Na diffusion by rational design of Si-based layered architectures.

By means of density functional theory, we systematically investigate the insertion and diffusion of Na and Li in layered Si materials (polysilane and H-passivated silicene), in comparison with bulk Si. It is found that Na binding and mobility can be significantly facilitated in layered Si structures. In contrast to the Si bulk, where Na insertion is energetically unfavorable, Na storage can be achieved in polysilane and silicene. The energy barrier for Na diffusion is reduced from 1.06 eV in the Si bulk to 0.41 eV in polysilane. The improvements in binding energetics and in the activation energy for Na diffusion are attributed to the large surface area and available free volume for the large Na cation. Based on these results, we suggest that polysilane may be a promising anode material for Na-ion and Li-ion batteries with high charge-discharge rates.

Physics of band-filling correction in defect calculations of solid-state materials.

In solid-state physics/chemistry, a precise understanding of defect formation and its impact on the electronic properties of wide-bandgap insulators is a cornerstone of modern semiconductor technology. However, complexities arise in the electronic structure theory of defect formation when the latter triggers partial occupation of the conduction/valence band, necessitating accurate post-process correction to the energy calculations. Herein, we dissect these complexities, focusing specifically on the post-process band-filling corrections, a crucial element that often demands thorough treatment in defect formation studies. We recognize the importance of these corrections in maintaining the accuracy of electronic properties predictions in wide-bandgap insulators and their role in reinforcing the importance of a reliable common reference state for defect formation energy calculations. We explored solutions such as aligning deep states and electrostatic potentials, both of which have been used in previous works, showing the effect of band alignment on defect formation energy. Our findings demonstrate that the impact of defect formation on electronic structure (even deep states) can be significantly dependent on the supercell size. We also show that within band-filling calculations, one needs to account for the possible change of electronic structure induced by defect formation, which requires sufficient convergence of electronic structure with supercell size. Thus, this work emphasizes the critical steps to accurately predict defect formation energy and paves the way for future research to overcome these challenges and advance the field with more efficient and reliable predictive models.

Enhanced Li adsorption and diffusion in single-walled silicon nanotubes: an ab initio study.

We report a first-principles investigation of Li adsorption and diffusion in single-walled Si nanotubes (SWSiNTs) of interest to Li-ion battery anodes. We calculate Li insertion characteristics in SWSiNTs and compare them with the respective ones in carbon nanotubes (CNTs) and other silicon nanostructures. From our calculations, SWSiNTs show higher reactivity toward the adsorption of Li adatoms than CNTs and Si nanoclusters. Considering the importance of Li kinetics, we demonstrate that the interior of SWSiNTs may serve as a fast Li diffusion channel. The important advantage of SWSiNTs over their carbon analogues is a sevenfold reduction in the energy barrier for the penetration of the Li atoms into the nanotube interior through the sidewalls. This prepossesses easier Li diffusion inside the tube and subsequent utilization of the interior sites, which enhances Li storage capacity of the system. The improvements in both Li uptake and Li mobility over their analogues support the great potential of SWSiNTs as Li-ion battery anodes.

Noble Gas Functional Defect with Unusual Relaxation Pattern in Solids.

The conventional understanding has always been that noble gases are chemically inert and do not affect materials properties. This belief has led to their use as a standard reference in various experimental applications through noble gas implantation. However, in our research, using first-principles calculations, we delve into the effects of noble gas defects on the properties of several functional oxides, thereby questioning this long-held assumption. We provide evidence that noble gases can indeed serve as functional defects. They have the potential to decentralize the localized defect states and prompt a shift of electrons from the localized state to the conduction band. Our investigation unveils that noble gas defects can indeed significantly alter the material properties. Thus, we underscore the importance of factoring in such defects when assessing material properties.