RESUMEN
The success of solid-state synthesis often hinges on the first intermediate phase that forms, which determines the remaining driving force to produce the desired target material. Recent work suggests that when reaction energies are large, thermodynamics primarily dictates the initial product formed, regardless of reactant stoichiometry. Here, we validate this principle and quantify its constraints by performing in situ characterization on 37 pairs of reactants. These experiments reveal a threshold for thermodynamic control in solid-state reactions, whereby initial product formation can be predicted when its driving force exceeds that of all other competing phases by ≥60 milli-electron volt per atom. In contrast, when multiple phases have a comparable driving force to form, the initial product is more often determined by kinetic factors. Analysis of the Materials Project data shows that 15% of possible reactions fall within the regime of thermodynamic control, highlighting the opportunity to predict synthesis pathways from first principles.
RESUMEN
Improving the mechanical strength of ceramic solid electrolytes such as lithium phosphorus sulfide families for pressure-driven dendrite blocking as well as reducing the electronic conductivity to prevent a dendrite formation inside the electrolytes are very important to extend the lifespan of all-solid-state lithium-metal batteries. Here, we propose a low-temperature solution-precipitation process to prepare polymer-solid electrolyte composites for a highly uniform polymer distribution in the electrolyte to enhance their mechanical strength and reduce their electronic conduction. The composites with up to 12 wt % of polymer are prepared, and the composites exhibit high ionic conductivities of up to 0.3 mS/cm. Furthermore, the electrochemical stability of the electrolyte composites on Li striping/plating cycles is investigated. We confirm that the proposed solution-precipitation process makes the composite much more stable than the bare solid electrolyte and causes them to outperform similar composites from the other existing preparation methods, such as mechanical mixing and solution dispersion.
RESUMEN
Advances in solid-state batteries have primarily been driven by the discovery of superionic conducting structural frameworks that function as solid electrolytes. We demonstrate the ability of high-entropy metal cation mixes to improve ionic conductivity in a compound, which leads to less reliance on specific chemistries and enhanced synthesizability. The local distortions introduced into high-entropy materials give rise to an overlapping distribution of site energies for the alkali ions so that they can percolate with low activation energy. Experiments verify that high entropy leads to orders-of-magnitude higher ionic conductivities in lithium (Li)-sodium (Na) superionic conductor (Li-NASICON), sodium NASICON (Na-NASICON), and Li-garnet structures, even at fixed alkali content. We provide insight into selecting the optimal distortion and designing high-entropy superionic conductors across the vast compositional space.
RESUMEN
The charging process of secondary batteries is always associated with a large volume expansion of the alloying anodes, which in many cases, develops high compressive residual stresses near the propagating interface. This phenomenon causes a significant reduction in the rate performance of the anodes and is detrimental to the development of fast-charging batteries. However, for the Na-Sn battery system, the residual stresses that develop near the interface are not stored, but are relieved by the generation of high-density dislocations in crystalline Sn. Direct-contact diffusion experiments show that these dislocations facilitate the preferential transport of Na and accelerate the Na diffusion into crystalline Sn at ultrafast rates via "dislocation-pipe diffusion". Advanced analyses are performed to observe the evolution of atomic-scale structures while measuring the distribution and magnitude of residual stresses near the interface. In addition, multi-scale simulations that combined classical molecular dynamics and first-principles calculations are performed to explain the structural origins of the ultrafast diffusion rates observed in the Na-Sn system. These findings not only address the knowledge gaps regarding the relationship between pipe diffusion and the diffusivity of carrier ions but also provide guidelines for the appropriate selection of anode materials for use in fast-charging batteries.
RESUMEN
The fabrication of battery anodes simultaneously exhibiting large capacity, fast charging capability, and high cyclic stability is challenging because these properties are mutually contrasting in nature. Here, we report a rational strategy to design anodes outperforming the current anodes by simultaneous provision of the above characteristics without utilizing nanomaterials and surface modifications. This is achieved by promoting spontaneous structural evolution of coarse Sn particles to 3D-networked nanostructures during battery cycling in an appropriate electrolyte. The anode steadily exhibits large capacity (â¼480 mAhg-1) and energy retention capability (99.9%) during >1500 cycles even at an ultrafast charging rate of 12â¯690 mAg-1 (15C). The structural and chemical origins of the measured properties are explained using multiscale simulations combining molecular dynamics and density functional theory calculations. The developed method is simple, scalable, and expandable to other systems and provides an alternative robust route to obtain nanostructured anode materials in large quantities.
RESUMEN
The diffusion of carrier ions in alloying anodes often develops compressive stresses in front of the propagating interface, suppressing the carrier-ion diffusion and limiting their full penetration into alloying anodes during battery cycles. This phenomenon, termed "self-limiting diffusion (SLD)", reduces the rate performance of batteries and hinders the full usage of anode materials. However, SLD is mitigated in some systems where tensile residual stresses develop at the interface, causing them to manifest significantly improved rate performance and energy capacity. Here, a comparative study of LiSi and NaSn systems to elucidate how the differing diffusion kinetics displayed by the two systems can influence SLD behaviors and the rate performance of batteries is performed. Experiments show that the Na diffusion into soft Sn crystals induces tensile stresses near the interface, promoting the nucleation of high-density dislocations. Thus-formed dislocations facilitate Na diffusion at ultrafast rates by providing pathways for dislocation pipe diffusion and alleviate SLD, making crystalline Sn suitable for fast-charging anode material. The outcomes of this study, while filling the knowledge gaps on the reasons for SLD, offer some guidelines for the appropriate choice of potential anode materials with superior rate performance and energy capacity suitable for future applications.
RESUMEN
High-rate performance and mechanical stability of anode materials are the two important characteristics that are necessary to develop fast-charging batteries with longevity. In the present study, we demonstrate that both high rate performance and mechanical stability of the anode can be achieved with the Na-Sn battery system. Experiments show that the sodiation rate in crystalline Sn (c-Sn) is 2-3 orders of magnitude faster than that reported for the Li-Si system. Furthermore, this extraordinary rate is nearly the same regardless of the orientation of c-Sn, which can improve the cycle life by retarding the pulverization of c-Sn. Two main microstructural features responsible for the observed characteristics are identified: (1) a transformation from crystalline to amorphous phase occurring at thin layers of c-Sn near the interfacial front and (2) pipe diffusion of Na through sodiation-induced dislocations. In this study, the observed behaviors are explained by elucidating the diffusion kinetics, whereas the associated mechanistic origins are analyzed by resolving the diffusion process of Na+ near the Na/Sn interface using atomic simulations.
RESUMEN
Sodiation was performed on crystalline Sn cylinders using an in situ electron microscope to evaluate the rate performance of the Sn anode by directly measuring the sodiation rate. We observed that the sodiation rate of the Sn anode is more than 2 orders of magnitude higher than the lithiation rate of the Si anode under the same conditions. This unprecedented rate displayed by the Na-Sn system is attributed to the bond characteristics and crystalline-to-amorphous transformation of the Sn crystal at the thin interface of the Na-Sn diffusion couple. Here, using atomic simulations, we explain how and why the Sn anode exhibits this high rate performance by resolving the diffusion process of Na ions in the Na-Sn interfacial region and the electron structure of the crystalline Sn. This work provides a useful insight into the use of Sn as an attractive anode material for realizing ultrafast-charging batteries for electric vehicles and mobile devices.
RESUMEN
Despite their large theoretical storage capability, Na-Sn batteries exhibit poor round-trip energy efficiencies as compared to Li-Si batteries. Here, we report the results of a comprehensive study to elucidate how and why Na-Sn batteries exhibit such a low energy efficiency. As a convincing evidence for this behavior, we observed that the resistivity of the Sn anode increased by 8 orders of magnitude during in situ sodiation experiments, which is attributed to the formation of electrically resistive Zintl ions in the sodiated Sn. Continual sodiation induced the development of residual stresses at the Sn anode and caused the distortion of Zintl ions from their ideal configuration. This distortion caused a change in the electronic structure, resulting in the increased resistivity of the sodiated Sn. Our findings offer some solutions that can be used to improve the energy efficiency of Na-Sn batteries.