From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries.

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure-property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg2+ (with time scales ranging from 0.5 µs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. This observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

Constructing Pure Si Anodes for Advanced Lithium Batteries.

ConspectusWith the escalating demands of portable electronics, electric vehicles, and grid-scale energy storage systems, the development of next-generation rechargeable batteries, which boasts high energy density, cost effectiveness, and environmental sustainability, becomes imperative. Accelerating these advancements could substantially mitigate detrimental carbon emissions. The pursuit of main objectives has kindled interest in pure silicon as a high-capacity electroactive material, capable of further enhancing the gravimetric and volumetric energy densities compared with traditional graphite counterparts. Despite such promising attributes, pure silicon materials face significant hurdles, primarily due to their drastic volumetric changes during the lithiation/delithiation processes. Volume changes give rise to severe side effects, such as fracturing, pulverization, and delamination, triggering rapid capacity decay. Therefore, mitigating silicon particle fracture remains a primary challenge. Importantly, nanoscale silicon (below 150 nm in size) has shown resilience to stresses induced by repeated volume changes, thereby highlighting its potential as an anode-active material. However, the volume expansion stress not only affects the internal structure of the particle but also disrupts the solid-electrolyte interphase (SEI) layer, formed spontaneously on the outer surface of silicon, causing adverse side reactions. Therefore, despite silicon nanoparticles offering new opportunities, overcoming the associated issues is of paramount importance.Thus, this Account aims to spotlight the significant strides made in the development of pure silicon anodes with particular attention to feature size. From the emergence of nanoscale silicon, the following nanotechnology played a crucial role in growing the particle through nano/microstructuring. Similarly, bulk silicon microparticles gradually surfaced with the post-engineering methods owing to their practical advantages. We briefly discuss the special characteristics of representative examples from bulk silicon engineering and nano/microstructuring, all aimed at overcoming intrinsic challenges, such as limiting large volume changes and stabilizing SEI formation during electrochemical cycling. Subsequently, we outline guidelines for advancing pure silicon anodes to incorporate high mass loading and high energy density. Importantly, these advancements require superior material design and the incorporation of exceptional battery components to ensure compatibility and yield synergistic effects. By broadening the cooperative strategies at the cell and system levels, we anticipate that this Account will provide an insightful analysis of pure silicon anodes and catalyze their practical applications in real battery systems.

Azacyclic Anchor-Enabled Cohesive Graphite Electrodes for Sustainable Anion Storage.

Advanced energy-storage devices are indispensable for expanding electric mobility applications. While anion intercalation-type redox chemistry in graphite cathodes has opened the path to high-energy-density batteries, surpassing the limited energy density of conventional lithium-ion batteries , a significant challenge remains: the large volume expansion of graphite upon anion intercalation. In this study, a novel polymeric binder and cohesive graphite cathode design for dual-ion batteries (DIBs) is presented, which exhibits remarkable stability even under high voltage conditions (>5 V). The innovative binder incorporates an acrylate moiety ensuring superior oxidative stability and self-healing features, along with an azide moiety, which allows for azacyclic covalent bonding with graphite and interchain crosslinking. A simple 1-h ultraviolet treatment is sufficient for binder fixation within the electrode, leading to the covalent bond formation with graphite and the creation of a robust three-dimensional network. This modification facilitates deeper and more reversible anion intercalation, leading to improved capacity, extended lifespan, and sustainable anion storage. The binder design, exhibiting exceptional adhesive properties and effective stress mitigation, enables the construction of ultrathick graphite cathodes. These findings provide valuable insights for the development of advanced binders, paving the way for high-performance DIBs.

Nonporous Oxide-Terminated Multicomponent Bulk Anode Enabling Energy-Dense Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are emerging as power sources for large-scale storage owing to their abundant and inexpensive sodium (Na) source, but their limited energy density hinders their commercialization. High-capacity anode materials, such as antimony (Sb), which are potential energy boosters for SIBs, suffer from battery degradation owing to large-volume-changes and structural instability. The rational design of bulk Sb-based anodes to enhance the initial reversibility and electrode density inevitably requires atomic- and microscale-considered internal/external buffering or passivation layers. However, unsuitable buffer engineering causes electrode degradation and lowers energy density. Herein, the rationally designed intermetallic inner and outer oxide buffers for bulk Sb anodes are reported. The two chemistries in the synthesis process provide an atomic-scale aluminum (Al) buffer within the dense microparticles and an external mechanically stabilizing dual oxide layer. The prepared nonporous bulk Sb anode maintained excellent reversible capacity at a high current density and Na-ion full battery evaluations with Na3V2(PO4)3 (NVP) showing negligible capacity decay over 100 cycles. The demonstrated buffer designs for commercially favorable micro-sized Sb and intermetallic AlSb shed light on the stabilization of high-capacity or large-volume-change electrode materials for various metal-ion rechargeable batteries.

Solar Biomass Reforming and Hydrogen Production with Earth-Abundant Si-Based Photocatalysts.

Efficient electrochemical hydrogen production and biomass refinery are crucial for the decarbonization of various sectors. However, their energy-intensive nature and low efficiency have hindered their practical application. In this study, earth-abundant and non-toxic photocatalysts that can produce hydrogen and reform biomass efficiently, utilizing unlimited solar energy, are presented. The approach involves using low-bandgap Si flakes (SiF) for efficient light-harvesting, followed by modification with Ni-coordinated N-doped graphene quantum dots (Ni-NGQDs) to enable efficient and stable light-driven biomass reforming and hydrogen production. When using kraft lignin as a model biomass, SiF/Ni-NQGDs facilitate record-high hydrogen productivity at 14.2 mmol gcat -1  h-1 and vanillin yield of 147.1 mg glignin -1 under simulated sunlight without any buffering agent and sacrificial electron donors. SiF/Ni-NQGDs can be readily recycled without any noticeable performance degradation owing to the prevention of deactivation of Si via oxidation. This strategy provides valuable insights into the efficient utilization of solar energy and practical applications of electro-synthesis and biomass refinement.

Multiscale Polymeric Materials for Advanced Lithium Battery Applications.

Riding on the rapid growth in electric vehicles and the stationary energy storage market, high-energy-density lithium-ion batteries and next-generation rechargeable batteries (i.e., advanced batteries) have been long-accepted as essential building blocks for future technology reaching the specific energy density of 400 Wh kg-1 at the cell-level. Such progress, mainly driven by the emerging electrode materials or electrolytes, necessitates the development of polymeric materials with advanced functionalities in the battery to address new challenges. Therefore, it is urgently required to understand the basic chemistry and essential research directions in polymeric materials and establish a library for the polymeric materials that enables the development of advanced batteries. Herein, based on indispensable polymeric materials in advanced high-energy-density lithium-ion, lithium-sulfur, lithium-metal, and dual-ion battery chemistry, the key research directions of polymeric materials for achieving high-energy-density and safety are summarized and design strategies for further improving performance are examined. Furthermore, the challenges of polymeric materials for advanced battery technologies are discussed.

Role of a Multivalent Ion-Solvent Interaction on Restricted Mg2+ Diffusion in Dimethoxyethane Electrolytes.

The diffusion behavior of Mg2+ in electrolytes is not as readily accessible as that from Li+ or Na+ utilizing PFG NMR, due to the low sensitivity, poor resolution, and rapid relaxation encountered when attempting 25Mg NMR. In MgTFSI2/DME solutions, "bound" DME (coordinating to Mg2+) and "free" DME (bulk) are distinguishable from 1H NMR. With the exchange rates between them obtained from 2D 1H EXSY NMR, we can extract the self-diffusivities of free DME and bound DME (which are equal to that of Mg2+) before the exchange occurs using PFG diffusion NMR measurements coupled with analytical formulas describing diffusion under two-site exchange. The high activation enthalpy for exhange (65-70 kJ/mol) can be explained by the structural change of bound DME as evidenced by its reduced C-H bond length. Comparison of the diffusion behaviors of Mg2+, TFSI-, DME, and Li+ reveals a relative restriction to Mg2+ diffusion that is caused by the long-range interaction between Mg2+ and solvent molecules, especially those with suppressed motions at high concentrations and low temperatures.

Dual Buffering Inverse Design of Three-Dimensional Graphene-Supported Sn-TiO2 Anodes for Durable Lithium-Ion Batteries.

Stable battery operation involving high-capacity electrode materials such as tin (Sn) has been plagued by dimensional instability-driven battery degradation despite the potentially accessible high energy density of batteries. Rational design of Sn-based electrodes inevitably requires buffering or passivation layers mostly in a multi-stacked manner with sufficient void inside the shells. However, undesirable void engineering incurs energy loss and shell fracture during the strong calendaring process. Here, this study reports an inverse design of freestanding 3D graphene electrodes sequentially passivated by capacity-contributing Sn and protective/buffering TiO2 . Monodisperse polymer bead templates coated with inner TiO2 and outer SnO2 layers generate regular macropores and 3D interconnected graphene framework while the inner TiO2 shell turns inside out to fully passivate the surface of Sn nanoparticles during the thermal annealing process. The prepared 3D freestanding electrodes are simultaneously buffered by electronically conductive and flexible graphene support and ion-permeable/mechanically stable TiO2 nanoshells, thus greatly extending the cycle life of batteries more than 5000 cycles at 5 C with a reversible capacity of ≈520 mAh g-1 with a high volumetric energy density.

Three-Dimensional Monolithic Organic Battery Electrodes.

Design of freestanding electrodes incorporated with redox-active organic materials has been limited by the poor intrinsic electrical conductivity and lack of methodology driving the feasible integration of conductive substrate and the organic molecules. Single-walled carbon nanotube (SWCNT) aerogels, which possess continuous network structure and high surface area, offer a three-dimensional electrically conducting scaffold. Here, we fabricate monolithic organic electrodes by coating a nanometer-scale imide-based network (IBN) that possesses abundant redox-active sites on the 3D SWCNT scaffold. The substantially integrated 3D monolithic organic electrodes sustain high electrical conductance through a 3D electronic pathway in their compressed form (∼21 µm). A thin and controllable layer (<8 nm) of IBN organic materials has a strong adhesion onto the ultra-lightweight and conductive substrate and facilitates multielectron redox reactions to deliver a specific capacity of up to 1550 mA h g-1 (corresponding to the areal capacity of ∼2.8 mA h cm-2). The redox-active IBN in synergy with the 3D SWCNT scaffold can enable superior electrochemical performances compared to the previously reported organic-based electrode architectures and inorganic-based electrodes.

Atomic-scale combination of germanium-zinc nanofibers for structural and electrochemical evolution.

Alloys are recently receiving considerable attention in the community of rechargeable batteries as possible alternatives to carbonaceous negative electrodes; however, challenges remain for the practical utilization of these materials. Herein, we report the synthesis of germanium-zinc alloy nanofibers through electrospinning and a subsequent calcination step. Evidenced by in situ transmission electron microscopy and electrochemical impedance spectroscopy characterizations, this one-dimensional design possesses unique structures. Both germanium and zinc atoms are homogenously distributed allowing for outstanding electronic conductivity and high available capacity for lithium storage. The as-prepared materials present high rate capability (capacity of ~ 50% at 20 C compared to that at 0.2 C-rate) and cycle retention (73% at 3.0 C-rate) with a retaining capacity of 546 mAh g-1 even after 1000 cycles. When assembled in a full cell, high energy density can be maintained during 400 cycles, which indicates that the current material has the potential to be used in a large-scale energy storage system.

Infinitesimal sulfur fusion yields quasi-metallic bulk silicon for stable and fast energy storage.

A fast-charging battery that supplies maximum energy is a key element for vehicle electrification. High-capacity silicon anodes offer a viable alternative to carbonaceous materials, but they are vulnerable to fracture due to large volumetric changes during charge-discharge cycles. The low ionic and electronic transport across the silicon particles limits the charging rate of batteries. Here, as a three-in-one solution for the above issues, we show that small amounts of sulfur doping (<1 at%) render quasi-metallic silicon microparticles by substitutional doping and increase lithium ion conductivity through the flexible and robust self-supporting channels as demonstrated by microscopy observation and theoretical calculations. Such unusual doping characters are enabled by the simultaneous bottom-up assembly of dopants and silicon at the seed level in molten salts medium. This sulfur-doped silicon anode shows highly stable battery cycling at a fast-charging rate with a high energy density beyond those of a commercial standard anode.

Ultrafast-Charging Silicon-Based Coral-Like Network Anodes for Lithium-Ion Batteries with High Energy and Power Densities.

Fast charging rate and large energy storage are becoming key elements for the development of next-generation batteries, targeting high-performance electric vehicles. Developing electrodes with high volumetric and gravimetric capacity that could be operated at a high rate is the most challenging part of this process. Using silicon as the anode material, which exhibits the highest theoretical capacity as a lithium-ion battery anode, we report a binder-free electrode that interconnects carbon-sheathed porous silicon nanowires into a coral-like network and shows fast charging performance coupled to high energy and power densities when integrated into a full cell with a high areal capacity loading. The combination of interconnected nanowires, porous structure, and a highly conformal carbon coating in a single system strongly promotes the reaction kinetics of the electrode. This leads to fast-charging capability while maintaining the integrity of the electrode without structural collapse and, thus, stable cycling performance without using binder and conductive additives. Specifically, this anode shows high specific capacities (over 1200 mAh g-1) at an ultrahigh charging rate of 7 C over 500 charge-discharge cycles. When coupled with a commercial LiCoO2 or LiFePO4 cathode in a full cell, it delivers a volumetric energy density of 1621 Wh L-1 with a LiCoO2 cathode and a power density of 7762 W L-1 with a LiFePO4 cathode.

Mechanical mismatch-driven rippling in carbon-coated silicon sheets for stress-resilient battery anodes.

High-theoretical capacity and low working potential make silicon ideal anode for lithium ion batteries. However, the large volume change of silicon upon lithiation/delithiation poses a critical challenge for stable battery operations. Here, we introduce an unprecedented design, which takes advantage of large deformation and ensures the structural stability of the material by developing a two-dimensional silicon nanosheet coated with a thin carbon layer. During electrochemical cycling, this carbon coated silicon nanosheet exhibits unique deformation patterns, featuring accommodation of deformation in the thickness direction upon lithiation, while forming ripples upon delithiation, as demonstrated by in situ transmission electron microscopy observation and chemomechanical simulation. The ripple formation presents a unique mechanism for releasing the cycling induced stress, rendering the electrode much more stable and durable than the uncoated counterparts. This work demonstrates a general principle as how to take the advantage of the large deformation materials for designing high capacity electrode.

Directed Self-Assembly of Asymmetric Block Copolymers in Thin Films Driven by Uniaxially Aligned Topographic Patterns.

We present a simple, versatile approach to generate highly ordered nanostructures of block copolymers (BCPs) using rubbed surfaces. A block of poly(tetrafluoroethylene) (PTFE) was dragged across a flat substrate surface above the melting point of PTFE transferring a highly aligned PTFE topographic pattern to the substrate. Si wafer, glass, and polyimide films were used as substrates. Thin films of cylinder-forming asymmetric polystyrene-block-poly(2-vinylpyridine) copolymers (S2VPs) were solvent annealed on the surfaces having the transferred surface pattern to induce their directed self-assembly. Cylinders of P2VP oriented normal to the surface are markedly aligned along the rubbing direction and used as templates to generate extremely uniform arrays of various metallic nanoparticles of gold, silver, and platinum over a large area.

Folding Graphene Film Yields High Areal Energy Storage in Lithium-Ion Batteries.

We show that a high energy density can be achieved in a practical manner with freestanding electrodes without using conductive carbon, binders, and current collectors. We made and used a folded graphene composite electrode designed for a high areal capacity anode. The traditional thick graphene composite electrode, such as made by filtering graphene oxide to create a thin film and reducing it such as through chemical or thermal methods, has sluggish reaction kinetics. Instead, we have made and tested a thin composite film electrode that was folded several times using a water-assisted method; it provides a continuous electron transport path in the fold regions and introduces more channels between the folded layers, which significantly enhances the electron/ion transport kinetics. A fold electrode consisting of SnO2/graphene with high areal loading of 5 mg cm-2 has a high areal capacity of 4.15 mAh cm-2, well above commercial graphite anodes (2.50-3.50 mAh cm-2), while the thickness is maintained as low as ∼20 µm. The fold electrode shows stable cycling over 500 cycles at 1.70 mA cm-2 and improved rate capability compared to thick electrodes with the same mass loading but without folds. A full cell of fold electrode coupled with LiCoO2 cathode was assembled and delivered an areal capacity of 2.84 mAh cm-2 after 300 cycles. This folding strategy can be extended to other electrode materials and rechargeable batteries.

Multiscale Hyperporous Silicon Flake Anodes for High Initial Coulombic Efficiency and Cycle Stability.

Three-dimensional (3D) hyperporous silicon flakes (HPSFs) are prepared via the chemical reduction of natural clay minerals bearing metal oxides. Natural clays generally have 2D flake-like structures with broad size distributions in the lateral dimension and varied thicknesses depending on the first processing condition from nature. They have repeating layers of silicate and metal oxides in various ratios. When the clay mineral is subjected to a reduction reaction, metal oxide layers can perform a negative catalyst for absorbing large amounts of exothermic heat from the reduction reaction of the silicate layers with metal reductant. Selectively etching out metal oxides shows a hyperporous nanoflake structure containing 100 nm macropores and meso-/micropores on its framework. The resultant HPSFs are demonstrated as anode materials for lithium-ion batteries. Compared to conventional micro-Si anodes, HPSFs exhibit exceptionally high initial Coulombic efficiency over 92%. Furthermore, HPSF anodes show outstanding cycling performance (reversible capacity of 1619 mAh g-1 at a rate of 0.5 C after 200 cycles, 95.2% retention) and rate performance (∼580 mAh g-1 at a rate of 10 C) owing to their distinctive structure.

A multi-stacked hyperporous silicon flake for highly active solar hydrogen production.

3D multi-stacked hyperporous silicon flakes (MHSFs) are prepared via a selective chemical reduction of natural clay minerals bearing MgO negative catalyst layers. The resultant MHSFs are used as a photocatalyst for solar-driven hydrogen evolution and exhibit the highest photocatalytic acitivty (1031 µmol H2 h(-1) g(-1) Si) coupled with a Pt cocatalyst.

Revisiting Surface Modification of Graphite: Dual-Layer Coating for High-Performance Lithium Battery Anode Materials.

Surface modification of electrode active materials has garnered considerable attention as a facile way to meet stringent requirements of advanced lithium-ion batteries. Here, we demonstrated a new coating strategy based on dual layers comprising antimony-doped tin oxide (ATO) nanoparticles and carbon. The ATO nanoparticles are synthesized via a hydrothermal method and act as electronically conductive/electrochemically active materials. The as-synthesized ATO nanoparticles are introduced on natural graphite along with citric acid used as a carbon precursor. After carbonization, the carbon/ATO-decorated natural graphite (c/ATO-NG) is produced. In the (carbon/ATO) dual-layer coating, the ATO nanoparticles coupled with the carbon layer exhibit unprecedented synergistic effects. The resultant c/ATO-NG anode materials display significant improvements in capacity (530 mA h g(-1) ), cycling retention (capacity retention of 98.1 % after 50 cycles at a rate of C/5), and low electrode swelling (volume expansion of 38 % after 100 cycles) which outperform that of typical graphite materials. Furthermore, a full-cell consisting of a c/ATO-NG anode and an LiNi0.5 Mn1.5 O4 cathode presents excellent cycle retention (capacity retention of >80 % after 100 cycles). We envision that the dual-layer coating concept proposed herein opens a new route toward high-performance anode materials for lithium-ion batteries.

Generalized Redox-Responsive Assembly of Carbon-Sheathed Metallic and Semiconducting Nanowire Heterostructures.

One-dimensional metallic/semiconducting materials have demonstrated as building blocks for various potential applications. Here, we report on a unique synthesis technique for redox-responsive assembled carbon-sheathed metal/semiconducting nanowire heterostructures that does not require a metal catalyst. In our approach, germanium nanowires are grown by the reduction of germanium oxide particles and subsequent self-catalytic growth during the thermal decomposition of natural gas, and simultaneously, carbon sheath layers are uniformly coated on the nanowire surface. This process is a simple, reproducible, size-controllable, and cost-effective process whereby most metal oxides can be transformed into metallic/semiconducting nanowires. Furthermore, the germanium nanowires exhibit stable chemical/thermal stability and outstanding electrochemical performance including a capacity retention of ∼96% after 1200 cycles at the 0.5-1C rate as lithium-ion battery anode.