Cation Distribution Research Articles

Inhibiting Cation Segregation to Enable Highly Efficient Perovskite Light‐Emitting Diodes

AbstractPerovskite light‐emitting diodes (PeLEDs) present potential applications for next‐generation displays due to their excellent luminescent properties and solution processing. The formamidinium‐caesium lead bromide (FAxCs1−xPbBr3) mixed cation strategy is one of the primary methods to achieve high‐performance of Cs‐dominate PeLEDs system. However, the inhomogeneous distribution of cations is detrimental to the photoelectronic performance of Cs‐dominated PeLEDs. Here, in mixed FA/Cs perovskite films, it is observed that Cs, Br and trace Pb elements precipitated on the surface of the perovskite films. It is found that the segregation of cations is induced by the uncontrollable crystallization process of Cs/FA cations. By introducing biuret additive, the hydrogen bonding interaction of biuret and FA cation balances crystallization rate, which therefore significantly improves the crystal quality and cations distribution of perovskite films. As a result, green PeLEDs with a high external quantum efficiency of 28.8% are obtained, and represent five times enhancement in half‐life time (T50) of 2.48 h at an initial luminance of 100 cd m−2 relative to the control device. The results help to understand the relationship between cationic distribution and PeLEDs properties, offering significant insights for modulating the performance of PeLEDs.

Cerium doped superparamagnetic Mn-Zn ferrite as a promising material for self-regulated magnetic hyperthermia

Recently, cubic ferrites (CF) have been widely explored in biomedical applications, especially those that display superparamagnetism behavior due to the desirable absence of remanent field. In this study, we report the self-stabilization of the magnetic fluid hyperthermia (MFH) temperature in the cancer therapy range (42 - 48 ºC) by Ce3+ substitution in superparamagnetic Mn0.8Zn0.2Fe2-xCexO4 ferrite with x = 0.0; 0.015; 0.030; 0.050 and 0.100. A comprehensive characterization was performed in order to investigate the influence of this replacement on the magnetic and structural properties of the ferrite. The samples were synthesized by the sol-gel auto-combustion method and the properties were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), Raman spectroscopy (RS), Mössbauer spectroscopy (MS), vibrational sample magnetometry (VSM), and ferromagnetic resonance (FMR). Magnetic hyperthermia essays were used to obtain the heat induction curves and calculate energy dissipation. We refined the XRD data by the Rietveld method to determine the cation distribution and calculate interionic parameters. Magnetic characterization confirms the superparamagnetic behavior at 300 K, which is expected from the TEM results that show a narrow distribution of particle sizes, with a mean size of about 6.5 nm for all samples. The VSM results show a consistent decrease in magnetization saturation with cerium content that result in a weaker self-heating induction capacity for the cerium-doped samples. FMR results also show a smaller relaxation time T2 for these samples, suggesting a slower energy dissipation rate. These conclusions are confirmed by the heat induction curves and the values of the specific absorption rate (SAR), which are smaller for cerium-doped samples. For the a field with an amplitude of 35.33 kA/m and a frequency of 222 kHz, the temperature of the cerium-doped samples saturates in the optimum interval for cancer treatment, between 42 and 48 ºC. These results suggest that Ce3+ is a promising doping ion to optimize the heating rate behavior of Mn-Zn ferrite for cancer treatment by hyperthermia.

Design and characterization of defined alpha-helix mini-proteins with intrinsic cell permeability

Proteins with intrinsic cell permeability that can access intracellular targets represent a promising strategy for novel drug development; however, a general design principle is still lacking. Here, we established a library of 46,678 de novo-designed mini-proteins and performed cell permeability screening via phage display. Analyses revealed a characteristic neighboring distribution of positive charges across helices among enriched mini-proteins of CPP7, CPP11, CPP55, CPP109 and CPP112. Compared with the state-of-the-art cell-penetrating mini-protein ZF5.3, the optimized mini-protein CPP11D36R exhibited a sevenfold increase in cell permeability. Endocytosis uptake and early endosome release are the key penetrating mechanisms. A machine learning model with high-throughput data achieved an F1 score of 0.41, significantly outperforming the previously reported CPP prediction models, including MLACP, CPPpred and CellPPD, by 41 %. Overall, our findings validate the effectiveness of a helical structure with a cationic distribution as a design principle on a large scale and present a robust approach for the development of cell-permeable mini-protein drugs.

Structural evolution and magnetic, optical, and optoelectronic properties changes in annealed Co0.5Sr0.5Fe2O4 nanoparticles: A comprehensive study

A sample of Co0.5Sr0.5Fe2O4 nanoparticles was synthesized by the coprecipitation technique to explore the effect of annealing on the structure and some physical properties of the produced material. The coprecipitated sample consists of an orthorhombic strontium carbonate phase and the required cubic Co0.5Sr0.5Fe2O4. Annealing at elevated temperatures (900 °C) leads to the formation of cubic and hexagonal phases. This crystal structure was confirmed by X-ray diffraction analysis (XRD). The accuracy of the cation distribution of the cubic phase determined from the Rietveld analysis of XRD patterns is demonstrated by matching the experimental and theoretical lattice constants. There are several noticeable changes in aspects as the annealing temperature goes up. The transmission electron microscopy (TEM) images indicated that heating substantially affects the growth and densification of the smaller nanoparticles. There is a drop in the longitudinal and transverse wave velocities, bulk, rigidity, Young's moduli, Poisson ratio (σ), and Debye temperature (θD) with annealing and grain growth. The saturation magnetization and coercive field are enhanced with annealing. The particle size distribution calculated from TEM is confirmed and supported by the switching field distribution. The indirect optical bandgap energy (Eg) decreased with annealing. The present study concentrated on the thermal treatment impacts on various optical parameters, such as the refractive index and extinction coefficient. The optoelectrical parameters, such as the dielectric constant, dielectric loss, and optical and electrical conductivity, were extensively investigated, giving valuable insights, and their results were interpreted. These findings suggest potential applications in magnetic storage, sensors, and optoelectronics fields.

Dissymmetrization in eudialyte-group minerals. I. A model of ordered cation arrangement in the crystal structure of amableite-(Ce) using the P3 symmetry

The crystal structure of the recently discovered eudialyte group mineral, amabellite-(Ce) Na15[(Ce1.5Na1.5)Mn3]Mn2Zr3£Si[Si24O69(OH)3](OH)2 · H2O, found in the hyperagpaitic pegmatite of the Saint-Amable massif (Canada), has been solved by X-ray structural analysis within the space group R3. Amabellite-(Ce) is a member of the eudialyte group with the lowest calcium content and differs from other members of this group by the dominance of lanthanides in the part of the edge-sharing octahedra of the six-membered ring. The unit cell parameters of the mineral are: a = 14.1340(2), c = 30.378(1) Å, V = 5255.6(3) ų. A model of the cation distribution in the crystal structure of amabellite-(Ce) within the low-symmetry space group P3 has been proposed. The obtained 162 independent positions were refined in the isotropic-anisotropic approximation of atomic displacements using 3968 F 3σ(F), R = 4.6%. Despite the fairly close results, the transition from space group R3 to P3 allows for more detailed information on the local distribution of a number of elements over the framework positions. A comparison was made between the crystal structure models of amabellite within the symmetries R3 and P3, as well as other low-calcium eudialyte group minerals previously studied within several space groups.

Single-Nanometer Spinel with Precise Cation Distribution for Enhanced Oxygen Reduction.

Designing spinel nanocrystals (NCs) with tailored structural composition and cation distribution is crucial for superior catalytic performance but remarkably challenging due to their intricate nature. Here, an aggregation growth restricted hot-injection method is presented by meticulously investigating the fundamental nucleation and aggregation-driven growth kinetics governing spinel NC formation to address this challenge. Through controlled collision probability of nuclei during growth, this approach enables the synthesis of spinel NCs with unprecedented, single nanometer (1.2nm). Single-nanometer CoMn2O4 spinel via this method exhibits a highly tailored structure with a maximized population of highly active octahedral Mn atoms, thereby optimizing oxygen intermediate adsorption during oxygen reduction reaction (ORR). Consequently, it exhibits a remarkable half-wave potential of 0.88V in ORR and leads to a superior power density (170.9mW cm-2) in zinc-air battery, outperforming commercial Pt/C and most reported spinel oxides, revealing a clear structure-property relationship. This structure design strategy is readily adaptable for the precise synthesis and engineering of various spinel structures, opening new avenues for developing advanced electrocatalysts and energy storage materials.

Fabrication of Nd-Ho Cosubstituted Co0.5Ni0.5Fe2O4 Nanospinel Ferrites and Exploration of Their Microstructure, Magnetic, and Electromagnetic Characteristics.

The composition and hyperfine structures of Nd3+-Ho3+ ions cosubstituted CoNi nanospinel ferrites (Co0.5Ni0.5NdxHoxFe2-2xO4 (x ≤ 0.05) NSFs) as well as their magnetic and electrodynamic behavior have been presented. The compound Nd-Ho → CoNiFe2O4 (x ≤ 0.05) NSFs were produced using the sol-gel method. XRD powder patterns indicated phase- and substituent-induced modifications of crystallites. The SEM analysis indicated the homogeneous distribution of grains with Nd-Ho cosubstitution. It was found that the values of x had an impact on the hyperfine magnetic field of the A and B sites. The cation distribution was determined by using Mössbauer spectroscopy. The M-H loops' investigations showed that the current NSFs behave ferrimagnetically at both room and low temperatures. An almost continuous rise in the strength of the coercive field was noticed with a rise in Ho-Nd content. The value of calculated squareness ratio values was above 0.5 at both temperatures, entailing that the studied NSFs' structure is made of single magnetic domains. The electromagnetic characteristics of the samples can be explained by the main contribution to electromagnetic absorption being the electric energy losses. Electromagnetic absorbed materials can be applied to provide electromagnetic compatibility and develop functional electromagnetic shields.

Anion Selectivities in Zwitterion Grafted Nanopores: Effect of Zwitterion Architecture.

The separation of ions of similar charge is a crucial challenge in many applications, from water treatment to precious metal recovery. Membranes with cross-linked zwitterionic amphiphilic copolymer (ZAC-X) selective layers, which feature self-assembled, zwitterion-lined nanodomains for permeation, offer unique permselectivity between monovalent anions (e.g., Cl-/F-). This has motivated studies on the mechanisms of transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the ZI ligands on anion diffusivities, partitioning, and permeabilities. Our model compares systems with contrasting ZI organization: surface-cation-anion (S-ZI+-ZI-, Motif A) and surface-anion-cation (S-ZI--ZI+, Motif B). Our results reveal that Motif A exhibits less pronounced ion pairing due to a spatial separation in the radial profiles of cations and anions. Motif B demonstrates prominent ion pairing for smaller anions owing to their overlap with cation distributions. Further, our potential of mean force profiles reveals that anion partitioning increases with anion size in both ligand motifs, whereas Motif B exhibits significantly higher partitioning selectivity toward larger anions compared to Motif A. Our results for ion diffusivities show that the self-diffusivities of both anions and cations are lower for Motif B compared to Motif A. Such trends in anion partitioning and diffusivities can be explained by differences in the interactions and steric hindrance experienced by the anionic species in Motifs A and B. Finally, our results for anion permselectivity, obtained by combining partitioning and diffusivity, indicate that partitioning trends dominate over diffusivity trends. Consequently, anion permeability increases with anion size, and ligand Motif B yields much higher permselectivity toward larger anions compared to ligand Motif A.

Origin of magnetism via cation vacancy defects in non-stoichiometric NiCo2O4 nanoparticles: A synchrotron-based x-ray absorption and x-ray magnetic circular dichroism spectroscopic study

The present study probes the effect of cation distributions in the structural, optical, electronic, and magnetic properties of mixed-valent inverse-spinel NiCo2O4 (NCO) nanoparticles (NPs). NCO NPs were prepared using the sol–gel combustion method and the grain size was obtained in the magnetic exchange length range assumed to be from single-ion anisotropy. The Raman and photoluminescence spectroscopies confirm the presence of an inverse-spinel structure with different oxidation states, and vibrating sample magnetometry clarifies the existence of ferromagnetism with the presence of magnetic anisotropy among the cations. These NPs annealed at a higher grain-growth temperature accumulate ferrimagnetic properties and produce magneto-crystalline anisotropy making NCO an assuring material for spintronic applications. A detailed x-ray absorption spectroscopy and x-ray magnetic circular dichroism studies reveal an indestructible correlation between the distribution of the present cations and the element-specific origin of ferrimagnetic behavior. Ni is found to be accountable for the magnetic moment and electronic conduction, whereas Co is associated mainly with the generation of the magnetic anisotropy even in the polycrystalline NP form. This describes the anti-ferromagnetic coupling between Co and Ni ions that is pivotal in demonstrating the exchange interaction between these cations. The above result signifies the site-dependent cation valence states for the magnetic properties, and the extent of growing conditions are related to such cation-site dysfunction. This depicts further tunability in NCO as a functional oxide material.

High-Entropy Selenides with Tunable Lattice Distortion as Efficient Electrocatalysts for Oxygen Evolution Reaction.

Developing stable and active electrocatalysts is crucial for enhancing the oxygen evolution reaction (OER) efficiency, which sluggish kinetics hinders sustainable hydrogen production. High entropy selenides (HESes) features with random distribution of multiple metals cations and unique electronic and size effect of Se anion, allowing for precious regulation of their catalytic properties towards high OER activity. In this work, we report a series of high-entropy selenides catalysts with tunable lattice strain for electrocatalytic oxygen evolution. Electrochemical measurements show that the quinary (NiCoMnMoFe)Sex requires only 291 mV to reach 10 mA cm-2 and exhibits a superior stability with negligible current decay during 100 h's continuous operation. By combining experimental measurements and theoretical calculation, the study reveals that the lattice distortion, reflected by the local microstrain near the active site, plays a vital role in boosting the OER activity of HESes.

Gradient distribution of cations in rhabdophane La0.27Y0.73PO4·nH2O nanoparticles

The structure of gradient rhabdophane nanoparticles of variable composition (La,Y)PO4·nH2O obtained by precipitation is considered. According to the data of HAADF TEM and EDX mapping using the Abel inversion procedure, it was shown that there is an inhomogeneous distribution of yttrium and lanthanum atoms in the particles from the central part to the periphery. At the same time, the nominal composition of both individual nanoparticles and the entire sample meets the value specified during synthesis within the error of the method – La0.27Y0.73PO4·nH2O. According to SAXS data, it was determined that in the particles of (La,Y)PO4·nH2O, there is a redistribution of scattering densities, which is caused by an increase in the fraction of YPO4 in the peripheral region of the particles. The observed effect of the distribution of cations over the particle made it possible to determine the size of the gradient layer, which reaches 50 % of the total particle size.

Controlling Chelation and Esterification in Pechini Synthesis for Enhancing Chemical Looping Steam Methane Reforming using LaFeO3 Perovskite.

The properties of an oxygen carrier, such as crystalline structure, textural properties, and surface chemical species, significantly influence the redox performance in thermochemical redox applications. This study presents the synthesis of various lanthanum orthoferrite (LaFeO3) perovskites by adjusting Pechini synthesis parameters, including chelating agent ratio, calcination temperature, and solution pH. A larger surface area emerged as a dominant factor contributing to improved redox performance. The porosity of the polyester resin proves crucial in achieving a large surface area and a small particle size for the oxygen carrier. This goal could be attained by controlling the pH of the precursor solution. A low degree of chelation or precipitation may lead to uneven cation distribution, resulting in the enrichment of trace hydroxide impurities. These impurities can suppress the reducibility of particles during the looping experiment. Various investigations, using XRD, XPS, XAS, SEM, and N2 physisorption, revealed that porosity and crystallinity can be controlled by altering the synthesis parameters.

Диссимметризация в минералах группы эвдиалита. IV. Особенности блочного изоморфизма в структуре Nb-дефицитного аналога онейллита в рамках P3-симметрии

The crystal structure of a potentially new member of the eudialyte group, the Nb-deficient analogue of oneillite from Mont Saint-Hilaire, Québec, Canada, with the idealized formula: Na13(Ca3Mn3)Zr3(Fe,Mn)3(,Nb)(Si,Nb,) [Si3O9]2[Si9O27]2(O,OH,Cl)3•2H2O, has been re-studied within the space group P3. The unit-cell parameters are: a = 14.134(3), c = 30.178(6) Å, V = 52201 Å3. The crystal structure of the mineral has been previously investigated using the space group R3 (typical for the members of oneillite family). In this work a structural model characterized by 155 crystallographic sites was solved in the frame of the low symmetry space group P3 and refined to R = 5.9 % using 4179 reflections with F > 2(F). The cation distribution between the key sites in low symmetry is more detailed.

Effect of γ-rays irradiation on the structural, magnetic, and electrochemical properties of ZnMn2O4 nanoparticles

The study explored the effect of gamma-ray irradiation on the physical, magnetic, and electrochemical properties of ZnMn2O4 synthesized by the burning method. On the physical characterization side, the study utilized multiple metrology techniques to determine the impact of radiation dosage on bond lengths, density, crystallite size, micro strain, lattice constant, and dislocation density. No irradiation impact on the sample's tetragonal spinel structure was observed up to 250 kGy doses. However, the lattice parameters increased post-γ-irradiation and were apparent in the morphology change of irradiated samples compared to control spinel. Conversely, the magnetic parameters decreased post-irradiation based on the vibrating-sample magnetometry (VSM) testing of control and γ-irradiated samples. Changes in parameters like saturation magnetization (Ms) and magneton number (nB) can be attributed to ion-induced disorder and cation distribution in irradiated samples. Finally, the electrochemical testing showed supercapacitor behavior for all ZnMn2O4 samples, with a positive impact of radiation on electrical capacitance and stability. While the γ-irradiated sample with a 250 kGy dose showed a capacitance (Csp) of 515 F/g with 87.6% stability, the control sample had a Csp of 123 F/g and 78% stability. ZnMn2O4 material meets the needs of energy storage devices operating at high ionizing radiation doses.

Optimization of Magnetite Nanoparticles for Magnetic Hyperthermia: Correlation with Physicochemical Properties and Cation Distribution

AbstractThe present study reveals the synthesis of Iron oxide nanoparticles (IONPs) by varying the molar ratio of ferric (Fe3+) to ferrous (Fe2+) ions via chemical coprecipitation method for the study of cationic distribution of Fe‐ions and its potential application for magnetic hyperthermia therapy (MHT). X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS), were used to characterize the physicochemical properties. Several structural parameters were estimated using the Rietveld refinement, resulting in structural modelling verified by magnetic characteristics. A vibrating sample magnetometer (VSM) assessed the magnetic hysteresis loop at room temperature in a field range of ±15 kOe, revealing superparamagnetic behavior for the ratio Fe2+/Fe3+ 1:2. The saturation magnetization (Ms) of IONPs increased with the increasing Fe2+ concentration and attained a maximum value of 60.21 emu g−1 at a molar ratio of 2:1. The potential of the inductive heating capability of IONPs in an alternating current magnetic field (AMF) was studied to treat localized MHT. The changes in magnetic properties and inductive heating properties of IONPs are associated with the cationic distribution of Fe2+ at the tetrahedral (A) and octahedral (B) sites of crystal structure. The variation in cationic properties at the A and B sites may result in varying/tuneable magnetic properties, affecting the overall heating profiles of hyperthermia.

Microwave absorption properties of ytterbium substituted X-type ferrite in P-, L-, S-, and C-band

Ba1.5Sr0.5Zn2Fe28-xYbxO46 (x = 0.00, 0.07, 0.14, 0.21, and 0.28) hexaferrite were synthesized via sol-gel auto-combustion route to investigate the microwave absorption performance in different frequency bands. The structure has a single phase, and the variation in lattice parameter was observed due to Yb-content as host iron Fe3+ and substituted Yb3+ having different ionic radii. Microwave absorbing materials (MAMs) need to be lightweight, and the maximum crystallite size of prepared material is 41 nm. The physical properties vary with substitution, and the X-ray density value is higher than the bulk density, and the porosity of the prepared sample increases when the bulk density decreases. Micro-strain values are inverse to the crystallite size because Yb3+ has larger ionic radii than Fe3+. Rietveld refinement of the XRD patterns was conducted with a lower significance value. FTIR bands observed between 414 and 500 cm−1 are present due to iron-oxygen bond stretching and bending vibrations at octahedral and tetrahedral lattice sites. The cation distribution is highly responsible for the peak position of octahedral and tetrahedral sites—the dielectric constant increases with frequency because of dipole, interfacial, and electronic/atomic polarization. AC conductivity is very low, reflecting that the material can be used as a dielectric medium in the microwave frequency range's L, S, and C bands. The best MAM among all prepared materials is Ba1.5Sr0.5Zn2Fe27.72Yb0.28O46 which can be used for global positioning systems, weather radar, and satellite feeds as it has an excellent dielectric loss, remarkable tangential loss, and the reflection loss in P-, L-, S-, and C-bands. Other real-life application of all prepared materials are multi-layer chip inductor and longitudinal media recording.

Fine structural analysis of calcium–niobium–gallium garnet (CNGG) by single-crystal anomalous X-ray scattering

Single-crystal anomalous X-ray scattering (AXS) experiments were conducted to investigate the cation distribution of calcium–niobium–gallium garnet (CNGG). AXS measurements suggested an ordered distribution of Nb at the octahedral site, and further structural refinement allowed us to obtain the structural formula Ca3Nb1.703(0) Ga3.162(2)O12. Ca was only located in the dodecahedral site, while Ga was distributed in the octa- and tetrahedral sites. The tetrahedral site had a significant number of vacancies at a ratio of one vacancy per unit cell, and the Nb/Ga occupation ratio at the octahedral site results in non-stoichiometric chemical composition of CNGG and its unique broad absorption wavelength.The findings of this study can contribute to device fabrication, property optimization, and quality control processes related to CNGG.

Efect of Li1+ ion on the physico-chemical properties cation distribution of sol-gel synthesized Ni-Zn spinel ferrite nanoparticles

Efect of Li1+ ion on the physico-chemical properties cation distribution of sol-gel synthesized Ni-Zn spinel ferrite nanoparticles

The Spatial Distribution of Lipophilic Cations in Gradient Copolymers Regulates Polymer-pDNA Complexation, Polyplex Aggregation, and Intracellular pDNA Delivery.

Here, we demonstrate that the spatial distribution of lipophilic cations governs the complexation pathways, serum stability, and biological performance of polymer-pDNA complexes (polyplexes). Previous research focused on block/statistical copolymers, whereas gradient copolymers, where the density of lipophilic cations diminishes (gradually or steeply) along polymer backbones, remain underexplored. We engineered gradient copolymers that combine the polyplex colloidal stability of block copolymers with the transfection efficiency of statistical copolymers. We synthesized length- and compositionally equivalent gradient copolymers (G1-G3) along with statistical (S) and block (B) copolymers of 2-(diisopropylamino)ethyl methacrylate and 2-hydroxyethyl methacrylate. We mapped how polymer microstructure governs pDNA loading per polyplex, pDNA conformational changes, and polymer-pDNA binding thermodynamics via static light scattering, circular dichroism spectroscopy, and isothermal titration calorimetry, respectively. While gradient steepness is a powerful design handle to improve polyplex physical properties, augment pDNA delivery capacity, and attenuate polycation-triggered hemolysis, microstructural contrasts did not elicit differences in complement activation.

Effect of Synthesis Conditions on the Composition, Local Structure and Electrochemical Behavior of (Cr,Fe,Mn,Co,Ni)3O4 Anode Material

AbstractDisordered high entropy spinels (HES) (Cr,Fe,Mn,Co,Ni)3O4 were obtained by solid‐state synthesis and co‐precipitation using various powder precursors. They were characterized by a complex of physico‐chemical methods and investigated as anode materials for lithium‐ion batteries (LIBs). According to XRD and TEM data, the materials are single‐phase. The structural characterization of the samples obtained at 773, 973, and 1273 K was determined using Raman and Mössbauer spectroscopy, and magnetic measurements. The degree of spinel inversion and lattice distortion (microstrains) decrease with increasing synthesis temperature, while the crystallite size increases. The insufficient nickel content in the samples ensures a more uniform distribution of iron cations in both sublattices, which leads to an increase in the lattice parameters and has a positive effect on the de‐/lithiation. Repeated ball‐milling of HES material, prepared by co‐precipitation, increases its specific capacity from 284 mAh g−1 to 492 mAh g−1 at a current density of 100 mA g−1 after 25 cycles. Besides, the smaller crystallite size reduces the volume changes in the materials during de‐/lithiation.