Which Interfaces Matter Most? Variability in Grain Boundary Defect Chemistry and Conductivity in a Concentrated Solid Electrolyte

Ionic conductivity of high-purity Gd-doped ceria solid solutions

Effects of dopant concentration and aging on the electrical properties of Y-doped ceria electrolytes

Garnet-type Li7La3Zr2O12 (LLZO) and its derivatives are considered promising candidate materials for all-solid-state Li-ion batteries as solid electrolytes due to their high Li+ conductivities of around 10-4 S cm-1 at room temperature and wide electrochemical window. Despite the larger number of detailed studies utilizing various experimental and theoretical approaches, the experimentally evaluated Li+ conductivities did not precisely match the computationally predicted values. The discrepancy between the ion conductivities can be attributed to the ambivalent properties of grain boundaries (GBs). GB structure is a critical parameter that controls the macroscopic properties of materials. However, various technological limitations of both the experimental and theoretical approaches utilized for elucidating the Li+ conduction behavior of GBs have restricted our ability of reaching a deeper understanding of the processes occurring at the atomic level. In this study, we investigated the Li+conducting behaviors of various tilted GBs of cubic LLZO with a garnet framework by using molecular dynamics approaches. Nine stoichiometric equilibrium GB models were used to determine Li+conductivity. It was found that the GB conductivity was smaller than the bulk one regardless of the orientation. In particular, the conductivities perpendicular to the GBs were characterized by the lowest values. Some factors affecting Li conductivity near the tilted GBs may be related to their stability. The relationship between the structural distortions at the GBs and the Li+ conducting characteristics were evaluated in terms of the GB energies and radial distribution function for the La-La, Zr-Zr, and O-O interactions in the LLZO bulk and GBs. We found that the Li+ conductivities are highly correlate with the structural distortions at the GBs. In order to elucidate the Li+ diffusion characteristics at the GBs in more detail, the variations of the atomic concentration near the GBs were calculated along the axis perpendicular to the GB surface. The atomic population at bulk region was constantly modulated, while that at GB region was anomalously dispersed. The average atomic concentration at the GBs was lower than that at the bulk. In particular, the observed decrease in the Li+ concentration suggests the formation of Li-deficient sites across the GB center, which represents the primary reason for the degraded ionic conductivity in the GB region. In fact, the Li ionic conductivity perpendicular to the GBs decreased with decreasing Li+ concentration at the GBs, which was caused by the slower diffusion of Li+. Thus, preventing the distortion of the GB crystallographic structure and the related drop in the Li+concentration should be considered one of the top priorities when designing GBs with desirable properties. Acknowledgement This work was partially supported by CREST, JST Grant Number JPMJCR1322, Japan.

Electrical and dielectric properties of polycrystalline VO2 discriminating between bulk and grain boundary conduction

<p indent="0mm">Since the commercialization of lithium-ion batteries in the 1990s, lithium-ion batteries have been successfully applied in portable electronics, electric vehicles, and grid energy storage. Although current organic liquid electrolytes have high ionic conductivities, they are inherently flammable, volatile, and prone to leakage. Moreover, severe side reactions and dendrite growth on the surface of the lithium anode during the charge-discharge process can cause safety hazards, which greatly impede their applications in lithium metal batteries. Solid electrolytes, including inorganic solid electrolytes and polymer electrolytes, are regarded as effective alternatives to organic liquid electrolytes for the construction of lithium metal batteries with high energy density and safety. Among them, solid polymer electrolytes offer excellent flexibility, processability, and interfacial compatibility over inorganic solid electrolytes, and they are extraordinarily promising for lithium metal batteries with high energy density and safety. Ideal solid polymer electrolytes should have following features: (1) High ionic conductivity (&gt; <sc>10 ^–4 S cm ^–1) </sc> at room temperature; (2) high lithium ion transference number (~1) to reduce the concentration polarization and improve the rate performance of batteries; (3) intimate contact at the electrode/electrolyte interfaces; (4) wide electrochemical window <sc>(&gt;4.5 V</sc> vs. Li/Li ⁺) to match high-voltage cathodes and improve the energy density of batteries; (5) good mechanical stability to resist processing, buffer electrode volume change and inhibit dendrite growth; (6) good thermal stability to withstand environmental changes. Generally, the ionic conductivity of pure solid polymer electrolytes at room temperature is low <sc>(~10 ^–6 S cm ^–1). </sc> Researchers have tried to improve the ionic conductivities by adjusting the lithium salt concentration, such as developing “polymer-in-salt” solid electrolytes. However, increasing the concentration of lithium salt leads to the deterioration of the mechanical strength. Strategies such as developing novel lithium salts, modifying polymer matrix, and incorporating inorganic fillers into solid polymer electrolytes are proposed to promote ionic conductivities of solid polymer electrolytes. In particular, composite polymer electrolytes, fabricated by dispersing a certain amount of inorganic fillers into solid polymer electrolytes, have improved ionic conductivities without sacrificing their mechanical performances. Poor interfacial property between electrodes and electrolytes is also a critical issue for solid polymer electrolytes. On one hand, poor and uneven solid/solid contacts at the electrode/electrolyte interfaces lead to high resistance and sluggish ionic transport kinetics. Furthermore, the volume change of the positive and negative electrodes in the charge/discharge process deteriorates the interfacial contacts, blocks the ion and electron transport through the interfaces, and greatly reduces the electrochemical reaction kinetics. On the other hand, the electrochemical windows of solid polymer electrolytes are usually narrow <sc>(＜4.5 V).</sc> During cycling, redox reactions are prone to occur at the electrode/electrolyte interfaces, causing battery failure. Solid polymer electrolytes have also poor thermal and mechanical stabilities. Therefore, design and synthesis of polymer-based solid electrolytes with excellent comprehensive performances and construction of fast and stable ion transport channels at the electrolyte/electrode interfaces are of great significance for the successful development of solid-state lithium metal batteries. This paper presents a brief review of the research progress in solid polymer electrolytes from two aspects: Improving the ionic conductivities of solid polymer electrolytes and enhancing the interfacial performance at electrolyte/electrode interfaces. First, targeted optimization strategies on ionic conductivities of solid polymer electrolytes, including constructing continuously aligned ionic transport paths and shortening the ionic transport distance, are summarized. Second, interface optimization strategies, including constructing wetting interfaces and synthesizing asymmetric electrolytes, are presented to reduce the interface resistance and improve the interfacial contact. Finally, perspectives on the development of solid polymer electrolytes and high-performance solid-state lithium metal batteries are discussed, and key research directions and advanced test methods are proposed. This review may provide a comprehensive understanding and further guidance for not only the material design of solid polymer electrolytes, but also the structural design of lithium metal batteries with favorable electrochemical and interfacial performances.

Currently, electrolytes used in lithium-ion batteries are flammable and leaky, causing safety problems when used under high temperatures or extreme conditions. Solid electrolytes can fundamentally avoid the occurrence of such issues, at the same time, it can significantly increase the energy density of solid state lithium batteries. Solid electrolytes are classified into inorganic solid electrolytes and solid polymer electrolytes. Although inorganic solid electrolytes have the high mechanical strength and room temperature ionic conductivity, it has poor flexibility and complicated preparation process. In contrast, solid polymer electrolyte has good elasticity and good interface contact, which can overcome many disadvantages of the inorganic solid electrolyte. Among them, polyethylene oxide (PEO) is first proposed as a polymer electrolyte. Due to its excellent mechanical properties, electrochemical stability and thermal stability, it has been a hot topic for polymer solid electrolytes for decades. However, its low room temperature ionic conductivity limits practical application. Given the problems existing in PEO-based polymer electrolytes, several methods for improving ionic conductivity have been proposed. The primary methods include plasticization, the organic-inorganic composite, and polymer blending. Comparing these methods, it can be seen that adding plasticizers to the polymer can effectively increase the conductivity of the electrolyte, but at the same time it will cause a decrease in the mechanical properties, and the safety issues limit its application in lithium-ion batteries. Inorganic fillers can balance the problems of ionic conductivity and mechanical properties, but the construction of a good filler-polymer dispersion system is complicated in preparing such composite electrolytes, design a new type of multi-dimensional the ion transport network also face tremendous challenges. Undoubtedly, in the future research, inorganic fillers will be the dominant means in the modification of composite electrolytes. Compared with the former two modification methods, polymer blending is easy to operate and friendly to industry, but low ionic conductivity at room temperature still exist. To give full play to the advantages of polymer blending, using it as an auxiliary means to improve the performance of composite electrolytes will be the primary development direction of such modification methods. PEO is the most widely studied polymer electrolyte. Even though a large number of modification methods have emerged in its development history, the ionic conductivity at room temperature is still limited to a relatively low level. To meet the needs of the application in lithium-ion batteries, a high operating temperature (50−70℃) is still needed, the biggest problem remains exist. To solve the problems in polymer solid electrolytes, the research directions in the future may mainly focus on: Expanding the modification method of PEO to other polymer electrolyte host materials, broadening the scope of research, and finding the available polymer electrolytes at room temperature. Concerned about the preparation of ultra-thin polymer electrolytes, reducing the ion transmission path to increase the transmission efficiency of lithium ions between positive and negative electrodes. Effectively combines inorganic solid electrolytes and solid polymer electrolytes to give full play to their advantages. In addition, exploring the effect of inorganic filler morphology on the conductivity of the composite electrolyte will also deserve attention. Many one-dimensional, two-dimensional materials can build ion transport networks so that lithium ions can travel rapidly along the path. With the deepening of research, it is expected that PEO-based polymer electrolytes may replace liquid electrolytes and become an essential cornerstone for building the next generation of safe and reliable lithium-ion batteries.

First-principles plane wave basis calculations were performed to investigate the atomic-scale mechanism of grain boundary (GB) sliding along the $\ensuremath{\Sigma}13$ pyramidal twin GB in $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Al}}_{2}{\mathrm{O}}_{3}$. It was found that the GB sliding takes place with successive breaking and rebonding of Al-O bonds across the GB core, and eventually results in migration of the GB plane. From detailed chemical bonding analyses, such atomic scale GB sliding behavior can be attributed to the bonding characteristics of individual Al-O pairs across the GB plane. These results suggest that the GB sliding behavior is strongly dependent on the character of Al-O bonding at the GB core.

Hydrogen as an interstitial solute at grain boundaries (GBs) can have a catastrophic impact on the mechanical properties of many metals. Despite the global research effort, the underlying hydrogen-GB interactions in polycrystals remain inadequately understood. In this study, using Voronoi tessellations and atomistic simulations, we elucidate the hydrogen segregation energy spectrum at the GBs of polycrystalline nickel by exploring all the topologically favorable segregation sites. Three distinct peaks in the energy spectrum are identified, corresponding to different structural fingerprints. The first peak (−0.205 eV) represents the most favorable segregation sites at GB core, while the second and third peaks account for the sites at GB surface. By incorporating a thermodynamic model, the spectrum enables the determination of the equilibrium hydrogen concentrations at GBs, unveiling a remarkable two to three orders of magnitude increase compared to the bulk hydrogen concentration reported in experimental studies. The identified structures from the GB spectrum exhibit vastly different behaviors in hydrogen segregation and diffusion, with the low-barrier channels inside GB core contributing to short-circuit diffusion, while the high energy gaps between GB and neighboring lattice serving as on-plane diffusion barriers. Mean square displacement analysis further confirms the findings, and shows that the calculated GB diffusion coefficient is three orders of magnitude greater than that of lattice. The present study has a significant implication for practical applications since it offers a tool to bridge the gap between atomic-scale interactions and macroscopic behaviors in engineering materials.

We present results of atomistic computer simulations of spontaneous and stress-induced grain boundary (GB) migration in copper. Several symmetrical tilt GBs have been studied using the embedded-atom method and molecular dynamics. The GBs are observed to spontaneously migrate in a random manner. This spontaneous GB motion is always accompanied by relative translations of the grains parallel to the GB plane. Furthermore, external shear stresses applied parallel to the GB and normal to the tilt axis induce GB migration. Strong coupling is observed between the normal GB velocity vn and the grain translation rate v||. The mechanism of GB motion is established to be local lattice rotation within the GB core that does not involve any GB diffusion or sliding. The coupling constant between vn and v|| predicted within a simple geometric model accurately matches the molecular dynamics observations.

ABSTRACTWe have carried out Monte Carlo (MC) simulations using the embedded atom potential to study the sliding and migration of the σ5 [001] (210) tilt grain boundary (GB) in aluminum and the effect of vacancies on the sliding properties. We find that the simulated annealing allows the system to gradually anneal to a global-minimum configuration, thus increasing the number of migrations and reducing the GB sliding energy barriers to about a factor of three compared to the corresponding “static” values. The distribution of atomic energies as a function of GB displacement, provide insight into which atoms are responsible for the GB migration. The vacancy formation energy is found to be lower when the vacancy is placed on the first layer to the boundary, in excellent agreement with ab initio electronic structure calculations. The sliding and migration properties depend very sensitively on the position of the vacancy in the GB core.

Absorption of edge dislocations in tilt grain boundaries (GBs) was studied by atomistic simulations in Al. The process of accommodation of dislocations in GBs and their evolution were analyzed based on atom rearrangement in GBs. It shows that the absorption is realized through both atom motion along the GB which is in perpendicular to the slip plane and structural neutralization of the dislocation core with the local GB core.

The atomic structure model of symmetric ［0001］tilt boundary of α phase in AZ91 magnesium alloy was set up by using the concept of coincidence-site lattice (CSL). The total structure energies of α matrix and grain boundary (GB), the environment sensitive embedding energies (EESE) and the interaction energies of Al, Bi and Sb were calculated by using recursion method. The alloying behaviour of Al, Bi, Sb in AZ91 magnesium alloy was discussed. Calculation results show that the total structure energies of α matrix and grain boundary (GB) are decreased due to the presence of Al, Bi or Sb, which suggests AZ91 alloy is strengthened due to solid solution strengthening. Alloying elements tend to be distributed uniformly in α matrix, and are apt to occupy the top sites of the trigonal prism formed by Mg in the GB core. The aggregation of Bi or Sb to GBs,being easier than Al, suppresses the aggregation of Al, which accelerates the formation of continuous precipitates, improves the high temperature properties. The major alloying element Al and the additional elements Bi or Sb in small amounts can form the ordered phases in AZ91 alloys: Mg１７Al１２, Mg3Bi2 and Mg３Sb２, respectively, and the quantity of the ordered phase is greater in GBs than in α(Mg) matrix. Bi or Sb additions to AZ91 retards the aggregation of Al, and Mg3Bi2 or Mg３Sb２ precipitates along boundaries greatly improve the high temperature properties.

The DMol molecular-cluster method, based on local density-functional theory, is employed to study the electronic structure and structural relaxation of a P impurity in the Fe \ensuremath{\Sigma}3[11\ifmmode\bar\else\textasciimacron\fi{}0](111) grain boundary (GB). Large clusters (53 and 91 atoms) are used to simulate the local environment of the Fe grain boundary; by calculating the force on the nearby Fe atoms around the impurity and minimizing the total energy of the cluster, an optimized atomic geometry with minimum energy is obtained. In the pure grain boundary, the center Fe atoms above the GB core have the tendency to move toward each other keeping a bond length very close to the Fe bulk bond length. From the 91-atom cluster, the P-induced relaxation of the Fe GB extends to at least eight Fe layers and the bond length between P and the nearest vertical Fe is 2.34 \AA{}, which is 3.5% larger than that in bulk ${\mathrm{Fe}}_{3}$P. Although the nearest Fe-P distance is the same in the vertical and horizontal directions, we found a stronger bonding between P and the in-plane Fe than in the vertical direction, which may contribute to the P embrittlement of Fe. A lesson from the present study with two cluster models is that even a cluster as large as 53 atoms does not provide the correct bonding picture around the impurity. This is due to the large relaxation induced by the P atom, which cannot be treated by a 53-atom cluster.

This paper presents several key aspects of the successful approach to preparing artificially-induced [001] tilt YBa{sub 2}Cu{sub 3}O{sub y} (YBCO) grain boundaries (GBs) with uniform, well-defined structures. The authors have compared the structure of GBs produced in thin film bicrystals and bulk bicrystals, respectively. In the YBCO thin film bicrystals prepared by off-axis magnetron sputtering, meandering rather than planar GBs were generally formed due to the three-dimensional island-shaped nucleation and growth of the thin films. Experimentally, using a low film deposition rate has been demonstrated to reduce the magnitude of meander. However, complete elimination of the meandering configuration has not yet been accomplished due to the film growth mechanism. Thus, the authors have developed a dual-seeded-melt-texture process to produce uniform, planar GBs in [001] tilt YBCO bulk bicrystals. Transmission electron microscopy (TEM) studies revealed GBs with a remarkably planar configuration on both micro and nano-meter scales, demonstrating that simpler, meander-free GB microstructures with well defined [001] tilt angle have been successfully produced compared to those formed in bicrystal thin films. The high reproducibility, excellent stability and well controlled GB orientations have established the dual-seeded-melt-texture process as a reliable technique for engineering artificial GBs for the purpose of systematic studies of GB properties and allow for more insightful measurements of transport properties across individual GBs.

Electrolytes are key components in electrochemical storage systems, which provide an ion-transport mechanism between the cathode and anode of a cell. As battery technologies are in continuous development, there has been growing demand for more efficient, reliable and environmentally friendly materials. Solid-state lithium ion batteries (SSLIBs) are considered as next-generation energy storage systems and solid electrolytes (SEs) are the key components for these systems. Compared to liquid electrolytes, SEs are thermally stable (safer), less toxic and provide a more compact (lighter) battery design. However, the main issue is the ionic conductivity, especially at low temperatures. So far, there are two popular types of SEs: (1) inorganic solid electrolytes (InSEs) and (2) polymer electrolytes (PEs). Among InSEs, sulfide-based SEs are providing very high ionic conductivities (up to 10−2 S/cm) and they can easily compete with liquid electrolytes (LEs). On the other hand, they are much more expensive than LEs. PEs can be produced at less cost than InSEs but their conductivities are still not sufficient for higher performances. This paper reviews the most efficient SEs and compares them in terms of their performances and costs. The challenges associated with the current state-of-the-art electrolytes and their cost-reduction potentials are described.