Alkali-Ion-Assisted Activation of ε-VOPO4 as a Cathode Material for Mg-Ion Batteries.

Rechargeable multivalent-ion batteries are attractive alternatives to Li-ion batteries to mitigate their issues with metal resources and metal anodes. However, many challenges remain before they can be practically used due to the low solid-state mobility of multivalent ions. In this study, a promising material identified by high-throughput computational screening is investigated, ε-VOPO4, as a Mg cathode. The experimental and computational evaluation of ε-VOPO4 suggests that it may provide an energy density of >200 Wh kg-1 based on the average voltage of a complete cycle, significantly more than that of well-known Chevrel compounds. Furthermore, this study finds that Mg-ion diffusion can be enhanced by co-intercalation of Li or Na, pointing at interesting correlation dynamics of slow and fast ions.

Sodium-Ion Battery: Can It Compete with Li-Ion?

As concerns about the availability of mineral resources for lithium-ion batteries (LIBs) arise and demands for large-scale energy storage systems rapidly increase, non-LIB technologies have been extensively explored as low-cost alternatives. Among the various candidates, sodium-ion batteries (SIBs) have been the most widely studied, as they avoid the use of expensive and less abundant elements such as lithium, cobalt, and nickel while also sharing similar operating principles with LIBs. In this Perspective, we discuss why SIBs hold great promise and can act as competitors to lithium-ion technology. In addition, the remaining challenges and future research directions are highlighted, focusing on cathode developments and the use of SIBs in large-scale applications, including electric vehicles and stationary energy storage.

An autonomous laboratory for the accelerated synthesis of novel materials.

To close the gap between the rates of computational screening and experimental realization of novel materials1,2, we introduce the A-Lab, an autonomous laboratory for the solid-state synthesis of inorganic powders. This platform uses computations, historical data from the literature, machine learning (ML) and active learning to plan and interpret the outcomes of experiments performed using robotics. Over 17 days of continuous operation, the A-Lab realized 41 novel compounds from a set of 58 targets including a variety of oxides and phosphates that were identified using large-scale ab initio phase-stability data from the Materials Project and Google DeepMind. Synthesis recipes were proposed by natural-language models trained on the literature and optimized using an active-learning approach grounded in thermodynamics. Analysis of the failed syntheses provides direct and actionable suggestions to improve current techniques for materials screening and synthesis design. The high success rate demonstrates the effectiveness of artificial-intelligence-driven platforms for autonomous materials discovery and motivates further integration of computations, historical knowledge and robotics.

Design principles for NASICON super-ionic conductors.

Na Super Ionic Conductor (NASICON) materials are an important class of solid-state electrolytes owing to their high ionic conductivity and superior chemical and electrochemical stability. In this paper, we combine first-principles calculations, experimental synthesis and testing, and natural language-driven text-mined historical data on NASICON ionic conductivity to achieve clear insights into how chemical composition influences the Na-ion conductivity. These insights, together with a high-throughput first-principles analysis of the compositional space over which NASICONs are expected to be stable, lead to the successful synthesis and electrochemical investigation of several new NASICONs solid-state conductors. Among these, a high ionic conductivity of 1.2 mS cm-1 could be achieved at 25 °C. We find that the ionic conductivity increases with average metal size up to a certain value and that the substitution of PO4 polyanions by SiO4 also enhances the ionic conductivity. While optimal ionic conductivity is found near a Na content of 3 per formula unit, the exact optimum depends on other compositional variables. Surprisingly, the Na content enhances the ionic conductivity mostly through its effect on the activation barrier, rather than through the carrier concentration. These deconvoluted design criteria may provide guidelines for the design of optimized NASICON conductors.

Lithium Phosphorus Sulfide Chloride-Polymer Composite via the Solution-Precipitation Process for Improving Stability toward Dendrite Formation of Li-Ion Solid Electrolyte.

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.

Lithium superionic conductors with corner-sharing frameworks.

Superionic lithium conductivity has only been discovered in a few classes of materials, mostly found in thiophosphates and rarely in oxides. Herein, we reveal that corner-sharing connectivity of the oxide crystal structure framework promotes superionic conductivity, which we rationalize from the distorted lithium environment and reduced interaction between lithium and non-lithium cations. By performing a high-throughput search for materials with this feature, we discover ten new oxide frameworks predicted to exhibit superionic conductivity-from which we experimentally demonstrate LiGa(SeO3)2 with a bulk ionic conductivity of 0.11 mS cm-1 and an activation energy of 0.17 eV. Our findings provide insight into the factors that govern fast lithium mobility in oxide materials and will accelerate the development of new oxide electrolytes for all-solid-state batteries.

Toward autonomous design and synthesis of novel inorganic materials.

Autonomous experimentation driven by artificial intelligence (AI) provides an exciting opportunity to revolutionize inorganic materials discovery and development. Herein, we review recent progress in the design of self-driving laboratories, including robotics to automate materials synthesis and characterization, in conjunction with AI to interpret experimental outcomes and propose new experimental procedures. We focus on efforts to automate inorganic synthesis through solution-based routes, solid-state reactions, and thin film deposition. In each case, connections are made to relevant work in organic chemistry, where automation is more common. Characterization techniques are primarily discussed in the context of phase identification, as this task is critical to understand what products have formed during synthesis. The application of deep learning to analyze multivariate characterization data and perform phase identification is examined. To achieve "closed-loop" materials synthesis and design, we further provide a detailed overview of optimization algorithms that use active learning to rationally guide experimental iterations. Finally, we highlight several key opportunities and challenges for the future development of self-driving inorganic materials synthesis platforms.

Synthetic accessibility and stability rules of NASICONs.

In this paper we develop the stability rules for NASICON-structured materials, as an example of compounds with complex bond topology and composition. By first-principles high-throughput computation of 3881 potential NASICON phases, we have developed guiding stability rules of NASICON and validated the ab initio predictive capability through the synthesis of six attempted materials, five of which were successful. A simple two-dimensional descriptor for predicting NASICON stability was extracted with sure independence screening and machine learned ranking, which classifies NASICON phases in terms of their synthetic accessibility. This machine-learned tolerance factor is based on the Na content, elemental radii and electronegativities, and the Madelung energy and can offer reasonable accuracy for separating stable and unstable NASICONs. This work will not only provide tools to understand the synthetic accessibility of NASICON-type materials, but also demonstrates an efficient paradigm for discovering new materials with complicated composition and atomic structure.

Insights into Layered Oxide Cathodes for Rechargeable Batteries.

Layered intercalation compounds are the dominant cathode materials for rechargeable Li-ion batteries. In this article we summarize in a pedagogical way our work in understanding how the structure's topology, electronic structure, and chemistry interact to determine its electrochemical performance. We discuss how alkali-alkali interactions within the Li layer influence the voltage profile, the role of the transition metal electronic structure in dictating O3-structural stability, and the mechanism for alkali diffusion. We then briefly delve into emerging, next-generation Li-ion cathodes that move beyond layered intercalation hosts by discussing disordered rocksalt Li-excess structures, a class of materials which may be essential in circumventing impending resource limitations in our era of clean energy technology.

Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries.

High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging class of solid solutions composed of a large number of species. These materials offer the benefit of large compositional flexibility and can be used in a wide variety of applications, including thermoelectrics, catalysts, superionic conductors and battery electrodes. We show here that the HE concept can lead to very substantial improvements in performance in battery cathodes. Among lithium-ion cathodes, cation-disordered rocksalt (DRX)-type materials are an ideal platform within which to design HE materials because of their demonstrated chemical flexibility. By comparing a group of DRX cathodes containing two, four or six transition metal (TM) species, we show that short-range order systematically decreases, whereas energy density and rate capability systematically increase, as more TM cation species are mixed together, despite the total metal content remaining fixed. A DRX cathode with six TM species achieves 307 mAh g-1 (955 Wh kg-1) at a low rate (20 mA g-1), and retains more than 170 mAh g-1 when cycling at a high rate of 2,000 mA g-1. To facilitate further design in this HE DRX space, we also present a compatibility analysis of 23 different TM ions, and successfully synthesize a phase-pure HE DRX compound containing 12 TM species as a proof of concept.

Promises and Challenges of Next-Generation "Beyond Li-ion" Batteries for Electric Vehicles and Grid Decarbonization.

The tremendous improvement in performance and cost of lithium-ion batteries (LIBs) have made them the technology of choice for electrical energy storage. While established battery chemistries and cell architectures for Li-ion batteries achieve good power and energy density, LIBs are unlikely to meet all the performance, cost, and scaling targets required for energy storage, in particular, in large-scale applications such as electrified transportation and grids. The demand to further reduce cost and/or increase energy density, as well as the growing concern related to natural resource needs for Li-ion have accelerated the investigation of so-called "beyond Li-ion" technologies. In this review, we will discuss the recent achievements, challenges, and opportunities of four important "beyond Li-ion" technologies: Na-ion batteries, K-ion batteries, all-solid-state batteries, and multivalent batteries. The fundamental science behind the challenges, and potential solutions toward the goals of a low-cost and/or high-energy-density future, are discussed in detail for each technology. While it is unlikely that any given new technology will fully replace Li-ion in the near future, "beyond Li-ion" technologies should be thought of as opportunities for energy storage to grow into mid/large-scale applications.

The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides.

In the synthesis of inorganic materials, reactions often yield non-equilibrium kinetic byproducts instead of the thermodynamic equilibrium phase. Understanding the competition between thermodynamics and kinetics is a fundamental step towards the rational synthesis of target materials. Here, we use in situ synchrotron X-ray diffraction to investigate the multistage crystallization pathways of the important two-layer (P2) sodium oxides Na0.67MO2 (M = Co, Mn). We observe a series of fast non-equilibrium phase transformations through metastable three-layer O3, O3' and P3 phases before formation of the equilibrium two-layer P2 polymorph. We present a theoretical framework to rationalize the observed phase progression, demonstrating that even though P2 is the equilibrium phase, compositionally unconstrained reactions between powder precursors favour the formation of non-equilibrium three-layered intermediates. These insights can guide the choice of precursors and parameters employed in the solid-state synthesis of ceramic materials, and constitutes a step forward in unravelling the complex interplay between thermodynamics and kinetics during materials synthesis.

Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries.

Structure plays a vital role in determining materials properties. In lithium ion cathode materials, the crystal structure defines the dimensionality and connectivity of interstitial sites, thus determining lithium ion diffusion kinetics. In most conventional cathode materials that are well-ordered, the average structure as seen in diffraction dictates the lithium ion diffusion pathways. Here, we show that this is not the case in a class of recently discovered high-capacity lithium-excess rocksalts. An average structure picture is no longer satisfactory to understand the performance of such disordered materials. Cation short-range order, hidden in diffraction, is not only ubiquitous in these long-range disordered materials, but fully controls the local and macroscopic environments for lithium ion transport. Our discovery identifies a crucial property that has previously been overlooked and provides guidelines for designing and engineering cation-disordered cathode materials.

Investigation of Potassium Storage in Layered P3-Type K0.5 MnO2 Cathode.

Novel and low-cost batteries are of considerable interest for application in large-scale energy storage systems, for which the cost per cycle becomes critical. Here, this study proposes K0.5 MnO2 as a potential cathode material for K-ion batteries as an alternative to Li technology. K0.5 MnO2 has a P3-type layered structure and delivers a reversible specific capacity of ≈100 mAh g-1 with good capacity retention. In situ X-ray diffraction analysis reveals that the material undergoes a reversible phase transition upon K extraction and insertion. In addition, first-principles calculations indicate that this phase transition is driven by the relative phase stability of different oxygen stackings with respect to the K content.

Reaction chemistry in rechargeable Li-O2 batteries.

The seemingly simple reaction of Li-O2 batteries involving lithium and oxygen makes this chemistry attractive for high-energy-density storage systems; however, achieving this reaction in practical rechargeable Li-O2 batteries has proven difficult. The reaction paths leading to the final Li2O2 discharge products can be greatly affected by the operating conditions or environment, which often results in major side reactions. Recent research findings have begun to reveal how the reaction paths may be affected by the surrounding conditions and to uncover the factors contributing to the difficulty in achieving the reactions of lithium and oxygen. This progress report describes the current state of understanding of the electrode reaction mechanisms in Li-O2 batteries; the factors that affect reaction pathways; and the effect of cell components such as solvents, salts, additives, and catalysts on the discharge product and its decomposition during charging. This comprehensive review of the recent progress in understanding the reaction chemistry of the Li-O2 system will serve as guidelines for future research and aid in the development of reliable high-energy-density rechargeable Li-O2 batteries.

A comparative study of graphite electrodes using the co-intercalation phenomenon for rechargeable Li, Na and K batteries.

Here, we demonstrate that graphite can serve as a versatile electrode for various rechargeable battery types by reversibly accommodating solvated alkali ions (such as K, Na, and Li) through co-intercalation in its galleries. The co-intercalation of alkali ions is observed to occur via staging reactions. Notably, their insertion behaviors, including their specific capacity, are remarkably similar regardless of the alkali ion species despite the different solubility limits of K, Na, and Li ions in graphite. Nevertheless, the insertion potentials of the solvated alkali ions differ from each other and are observed to be correlated with the interlayer distance in the intercalated graphite gallery.

Dissolution and ionization of sodium superoxide in sodium-oxygen batteries.

With the demand for high-energy-storage devices, the rechargeable metal-oxygen battery has attracted attention recently. Sodium-oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium-oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium-oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium-oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium-oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium-oxygen batteries to achieve high efficiency and rechargeability.

Sodium-Ion Storage in Pyroprotein-Based Carbon Nanoplates.

Pyroprotein-based carbon nanoplates are fabricated from self-assembled silk proteins as a versatile platform to examine sodium-ion storage characteristics in various carbon environments. It is found that, depending on the local carbon structure, sodium ions are stored via chemi-/physisorption, insertion, or nanoclustering of metallic sodium.

Facile Synthesis of Nb2O5@Carbon Core-Shell Nanocrystals with Controlled Crystalline Structure for High-Power Anodes in Hybrid Supercapacitors.

Hybrid supercapacitors (battery-supercapacitor hybrid devices, HSCs) deliver high energy within seconds (excellent rate capability) with stable cyclability. One of the key limitations in developing high-performance HSCs is imbalance in power capability between the sluggish Faradaic lithium-intercalation anode and rapid non-Faradaic capacitive cathode. To solve this problem, we synthesize Nb2O5@carbon core-shell nanocyrstals (Nb2O5@C NCs) as high-power anode materials with controlled crystalline phases (orthorhombic (T) and pseudohexagonal (TT)) via a facile one-pot synthesis method based on a water-in-oil microemulsion system. The synthesis of ideal T-Nb2O5 for fast Li(+) diffusion is simply achieved by controlling the microemulsion parameter (e.g., pH control). The T-Nb2O5@C NCs shows a reversible specific capacity of ∼180 mA h g(-1) at 0.05 A g(-1) (1.1-3.0 V vs Li/Li(+)) with rapid rate capability compared to that of TT-Nb2O5@C and carbon shell-free Nb2O5 NCs, mainly due to synergistic effects of (i) the structural merit of T-Nb2O5 and (ii) the conductive carbon shell for high electron mobility. The highest energy (∼63 W h kg(-1)) and power (16 528 W kg(-1) achieved at ∼5 W h kg(-1)) densities within the voltage range of 1.0-3.5 V of the HSC using T-Nb2O5@C anode and MSP-20 cathode are remarkable.