Design and synthesis of multigrain nanocrystals via geometric misfit strain.

The impact of topological defects associated with grain boundaries (GB defects) on the electrical, optical, magnetic, mechanical and chemical properties of nanocrystalline materials1,2 is well known. However, elucidating this influence experimentally is difficult because grains typically exhibit a large range of sizes, shapes and random relative orientations3-5. Here we demonstrate that precise control of the heteroepitaxy of colloidal polyhedral nanocrystals enables ordered grain growth and can thereby produce material samples with uniform GB defects. We illustrate our approach with a multigrain nanocrystal comprising a Co3O4 nanocube core that carries a Mn3O4 shell on each facet. The individual shells are symmetry-related interconnected grains6, and the large geometric misfit between adjacent tetragonal Mn3O4 grains results in tilt boundaries at the sharp edges of the Co3O4 nanocube core that join via disclinations. We identify four design principles that govern the production of these highly ordered multigrain nanostructures. First, the shape of the substrate nanocrystal must guide the crystallographic orientation of the overgrowth phase7. Second, the size of the substrate must be smaller than the characteristic distance between the dislocations. Third, the incompatible symmetry between the overgrowth phase and the substrate increases the geometric misfit strain between the grains. Fourth, for GB formation under near-equilibrium conditions, the surface energy of the shell needs to be balanced by the increasing elastic energy through ligand passivation8-10. With these principles, we can produce a range of multigrain nanocrystals containing distinct GB defects.

Electrochemomechanical failure in layered oxide cathodes caused by rotational stacking faults.

Electrochemomechanical degradation is one of the most common causes of capacity deterioration in high-energy-density cathodes, particularly intercalation-based layered oxides. Here we reveal the presence of rotational stacking faults (RSFs) in layered lithium transition-metal oxides, arising from specific stacking sequences at different angles, and demonstrate their critical role in determining structural/electrochemical stability. Our combined experiments and calculations show that RSFs facilitate oxygen dimerization and transition-metal migration in layered oxides, fostering microcrack nucleation/propagation concurrently with cumulative electrochemomechanical degradation on cycling. We further show that thermal defect annihilation as a potential solution can suppress RSFs, reducing microcracks and enhancing cyclability in lithium-rich layered cathodes. The common but previously overlooked occurrence of RSFs suggests a new synthesis guideline of high-energy-density layered oxide cathodes.

In operando visualization of redox flow battery in membrane-free microfluidic platform.

Redox flow batteries (RFBs) are attractive large-scale energy storage techniques, achieving remarkable progress in performance enhancement for the last decades. Nevertheless, an in-depth understanding of the reaction mechanism still remains challenging due to its unique operation mechanism, where electrochemistry and hydrodynamics simultaneously govern battery performance. Thus, to elucidate the precise reactions occurring in RFB systems, an appropriate analysis technique that enables the real-time observation of electrokinetic phenomena is indispensable. Herein, we report in operando visualization and analytical study of RFBs by employing a membrane-free microfluidic platform, that is, a membrane-free microfluidic RFB. Using this platform, the electrokinetic investigations were carried out for the 5,10-bis(2-methoxyethyl)-5,10-dihydrophenazine (BMEPZ) catholyte, which has been recently proposed as a high-performance multiredox organic molecule. Taking advantage of the inherent colorimetric property of BMEPZ, we unravel the intrinsic electrochemical properties in terms of charge and mass transfer kinetics during the multiredox reaction through in operando visualization, which enables theoretical study of physicochemical hydrodynamics in electrochemical systems. Based on insights on the electrokinetic limitations in RFBs, we verify the validity of electrode geometry design that can suppress the range of the depletion region, leading to enhanced cell performance.

All-Graphene Quantum Dot-Derived Battery: Regulating Redox Activity Through Localized Subdomains.

In the quest for materials sustainability for grid-scale applications, graphene quantum dot (GQD), prepared via eco-efficient processes, is one of the promising graphitic-organic matters that have the potential to provide greener solutions for replacing metal-based battery electrodes. However, the utilization of GQDs as electroactive materials has been limited; their redox behaviors associated with the electronic bandgap property from the sp2 carbon subdomains, surrounded by functional groups, are yet to be understood. Here, the experimental realization of a subdomained GQD-based anode with stable cyclability over 1000 cycles, combined with theoretical calculations, enables a better understanding of the decisive impact of controlled redox site distributions on battery performance. The GQDs are further employed in cathode as a platform for full utilization of inherent electrochemical activity of bio-inspired redox-active organic motifs, phenoxazine. Using the GQD-derived anode and cathode, an all-GQD battery achieves a high energy density of 290 Wh kgcathode -1 (160 Wh kgcathode+anode -1 ), demonstrating an effective way to improve reaction reversibility and energy density of sustainable, metal-free batteries.

Coupling structural evolution and oxygen-redox electrochemistry in layered transition metal oxides.

Lattice oxygen redox offers an unexplored way to access superior electrochemical properties of transition metal oxides (TMOs) for rechargeable batteries. However, the reaction is often accompanied by unfavourable structural transformations and persistent electrochemical degradation, thereby precluding the practical application of this strategy. Here we explore the close interplay between the local structural change and oxygen electrochemistry during short- and long-term battery operation for layered TMOs. The substantially distinct evolution of the oxygen-redox activity and reversibility are demonstrated to stem from the different cation-migration mechanisms during the dynamic de/intercalation process. We show that the π stabilization on the oxygen oxidation initially aids in the reversibility of the oxygen redox and is predominant in the absence of cation migrations; however, the π-interacting oxygen is gradually replaced by σ-interacting oxygen that triggers the formation of O-O dimers and structural destabilization as cycling progresses. More importantly, it is revealed that the distinct cation-migration paths available in the layered TMOs govern the conversion kinetics from π to σ interactions. These findings constitute a step forward in unravelling the correlation between the local structural evolution and the reversibility of oxygen electrochemistry and provide guidance for further development of oxygen-redox layered electrode materials.

Versatile Redox-Active Organic Materials for Rechargeable Energy Storage.

With the ever-increasing demand on energy storage systems and subsequent mass production, there is an urgent need for the development of batteries with not only improved electrochemical performance but also better sustainability-related features such as environmental friendliness and low production cost. To date, transition metals that are sparse have been centrally employed in energy storage devices ranging from portable lithium ion batteries (e.g., cobalt and nickel) to large-scale redox flow batteries (e.g., vanadium). Toward the sustainable battery chemistry, there are ongoing efforts to replace the transition metal-based electrode materials in these systems to redox-active organic materials (ROMs). Most ROMs are composed of the earth abundant elements (e.g., carbon, nitrogen, oxygen, sulfur), thus are less restrained by the resource, and their production does not require high-energy consuming processes. Furthermore, the structural diversity and chemical tunability of organic compounds make them more attractive for the versatile design of future energy storage systems. Accordingly, the timely development of high-performance ROM-based electrodes would expedite the shift from the current resource-limited battery chemistry to more sustainable energy solutions.In this Account, we provide an overview of the endeavors to employ and develop ROMs as high-performance active materials for various battery systems. Diverse approaches will be introduced starting from the new ROM design mimicking the energy carrying molecules in biological metabolism to the chemical modifications to tailor the properties for specific battery systems. The molecular redesign of ROM, for example, can be carried out by substituting heteroatoms in the redox center, which leads to the enhancement of the redox potential by the inductive effect. Or, tailoring the ROM molecule by removing redox-inactive functionals results in a reduced molecular weight, thereby an increased specific capacity. The intrinsic limitations of ROMs, such as the low electrical conductivity and the dissolving nature, have been under extensive scrutiny; however, they can be partly addressed through efforts including intermolecular fusion and/or nanoscale hybridization with a conducting scaffold. On the other hand, this problematic dissolving nature of ROMs makes them appealing for some new battery configurations such as redox flow batteries that employ the liquid-state active materials. The high solubility and the stability of the ROM were found to be beneficial in attaining the enhanced energy density and the cycle stability of flow batteries, which could be further optimized by the chemical modifications of ROMs. Besides the role of active materials, the redox activity of ROMs has also enabled their use as catalysts to promote the electrode reaction in metal-air batteries. The redox capability of the ROM was often proven to be effective in the solution-based redox mediation that facilitates both the charging and discharging reaction in metal-air batteries. Finally, we conclude this account by proposing the future research directions regarding the fundamental electrochemistry and the further practical development of ROMs for the sustainable rechargeable energy storage.

Nanoscale Phenomena in Lithium-Ion Batteries.

The electrochemical properties and performances of lithium-ion batteries are primarily governed by their constituent electrode materials, whose intrinsic thermodynamic and kinetic properties are understood as the determining factor. As a part of complementing the intrinsic material properties, the strategy of nanosizing has been widely applied to electrodes to improve battery performance. It has been revealed that this not only improves the kinetics of the electrode materials but is also capable of regulating their thermodynamic properties, taking advantage of nanoscale phenomena regarding the changes in redox potential, solid-state solubility of the intercalation compounds, and reaction paths. In addition, the nanosizing of materials has recently enabled the discovery of new energy storage mechanisms, through which unexplored classes of electrodes could be introduced. Herein, we review the nanoscale phenomena discovered or exploited in lithium-ion battery chemistry thus far and discuss their potential implications, providing opportunities to further unveil uncharted electrode materials and chemistries. Finally, we discuss the limitations of the nanoscale phenomena presently employed in battery applications and suggest strategies to overcome these limitations.

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes.

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

Unveiling the Intrinsic Cycle Reversibility of a LiCoO2 Electrode at 4.8-V Cutoff Voltage through Subtractive Surface Modification for Lithium-Ion Batteries.

The thermodynamic instability of the LiCoO2 layered structure at >0.5Li extraction has been considered an obstacle for the reversible utilization of its near theoretical capacity at high cutoff voltage (>4.6 V vs Li/Li+) in lithium-ion batteries. Many previous studies have focused on resolving this issue by surface modification of LiCoO2, which has proven to be effective in suppressing phase transformation. To determine the extent to which surface protection of LiCoO2 is effective despite its thermodynamic instability and presumably incomplete reversibility involving the O1 phase, here we verify the intrinsic reversibility of bulk LiCoO2 with extended lithium extraction by ruling out the effect of a surface. Specifically, first, we show that, contrary to conventional belief, electrochemical cycling of LiCoO2 at a cutoff voltage of 4.8 V (vs Li/Li+) results in better cycle stability and lower polarizations than those at 4.6 V. We demonstrate, using an exhaustive suite of characterization tools, that the rapid cycle degradation under high-voltage cycling is mostly caused by the formation of a surface resistive layer; however, these damaged surfaces are leached out faster than they are accumulated above a certain potential, which results in superior cyclability compared with that achieved for less oxidative 4.6-V cycling. This beneficial leaching out of the resistive surface layer serves as a "subtractive" surface modification and plays a role in enhancing the cycle stability and is distinguished from conventional "additive" surface modification such as coating. This approach allows us to decouple factors of the bulk and surface degradations that contribute to the capacity fade and leads to the finding that, in the absence of a resistive surface, the capacity retention of a LiCoO2 electrode with 4.8-V cutoff cycling can be intrinsically high, indicating that the instability of the crystalline Li xCoO2 ( x < 0.5) has a limited effect on the cycle stability. Our findings also explain why the strategy of coating foreign materials on the surface of LiCoO2 can improve the high-voltage cycling to some extent despite the expected thermodynamic instability of the highly charged phase.

Planting Repulsion Centers for Faster Ionic Diffusion in Superionic Conductors.

The successful launch of solid-state batteries relies on the discovery of solid electrolytes with remarkably high ionic conductivity. Extensive efforts have identified several important superionic conductors (SICs) and broadened our understanding of their superionic conductivity. Herein, we propose a new design strategy to facilitate ionic conduction in SICs by planting immobile repulsion centers. Our ab initio molecular dynamics simulations on the model system Na11 Sn2 PS12 demonstrate that the sodium ionic conductivity can be increased by approximately one order of magnitude by simply doping large Cs ions as repulsion centers in the characteristic vacant site of Na11 Sn2 PS12 . Planting immobile repulsion centers locally induces the formation of high-energy sites, leading to a fast track for ionic conduction owing to the unique interactions among mobile ions in SICs. Seemingly non-intuitive approaches tailor the ionic diffusion by exploiting these immobile repulsion centers.

Anchored Mediator Enabling Shuttle-Free Redox Mediation in Lithium-Oxygen Batteries.

Redox mediators (RMs) are considered an effective countermeasure to reduce the large polarization in lithium-oxygen batteries. Nevertheless, achieving sufficient enhancement of the cyclability is limited by the trade-offs of freely mobile RMs, which are beneficial for charge transport but also trigger the shuttling phenomenon. Here, we successfully decoupled the charge-carrying redox property of RMs and shuttling phenomenon by anchoring the RMs in polymer form, where physical RM migration was replaced by charge transfer along polymer chains. Using PTMA (poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate)) as a polymer model system based on the well-known RM tetramethylpiperidinyloxyl (TEMPO), it is demonstrated that PTMA can function as stationary RM, preserving the redox activity of TEMPO. The efficiency of RM-mediated Li2 O2 decomposition remains remarkably stable without the consumption of oxidized RMs or degradation of the lithium anode, resulting in an improved performance of the lithium-oxygen cell.

Controlling Residual Lithium in High-Nickel (>90 %) Lithium Layered Oxides for Cathodes in Lithium-Ion Batteries.

The rampant generation of lithium hydroxide and carbonate impurities, commonly known as residual lithium, is a practical obstacle to the mass-scale synthesis and handling of high-nickel (>90 %) layered oxides and their use as high-energy-density cathodes for lithium-ion batteries. Herein, we suggest a simple in situ method to control the residual lithium chemistry of a high-nickel lithium layered oxide, Li(Ni0.91 Co0.06 Mn0.03 )O2 (NCM9163), with minimal side effects. Based on thermodynamic considerations of the preferred reactions, we systematically designed a synthesis process that preemptively converts residual Li2 O (the origin of LiOH and Li2 CO3 ) into a more stable compound by injecting reactive SO2 gas. The preformed lithium sulfate thin film significantly suppresses the generation of LiOH and Li2 CO3 during both synthesis and storage, thereby mitigating slurry gelation and gas evolution and improving the cycle stability.

Direct Observation of Redox Mediator-Assisted Solution-Phase Discharging of Li-O2 Battery by Liquid-Phase Transmission Electron Microscopy.

Li-O2 battery is one of the important next-generation energy storage systems, as it can potentially offer the highest theoretical energy density among battery chemistries reported thus far. However, realization of its high discharge capacity still remains challenging and is hampered by the nature of how the discharge products are formed, causing premature passivation of the air electrode. Redox mediators are exploited to solve this problem, as they can promote the charge transfer from electrodes to the solution phase. The mechanistic understanding of the fundamental electrochemical reaction involving the redox mediators would aid in the further development of Li-O2 batteries along with rational design of new redox mediators. Herein, we attempt to monitor the discharge reaction of a Li-O2 battery in real time by liquid-phase transmission electron microscopy (TEM). Direct in situ TEM observation reveals the gradual growth of toroidal Li2O2 discharge product in the electrolyte with the redox mediator upon discharge. Moreover, quantitative analyses of the growth profiles elucidate that the growth mechanism involves two steps: dominant lateral growth of Li2O2 into disclike structures in the early stage followed by vertical growth with morphology transformation into a toroidal structure.

Redox-Sensitive Facet Dependency in Etching of Ceria Nanocrystals Directly Observed by Liquid Cell TEM.

Defining the redox activity of different surface facets of ceria nanocrystals is important for designing an efficient catalyst. Especially in liquid-phase reactions, where surface interactions are complicated, direct investigation in a native environment is required to understand the facet-dependent redox properties. Using liquid cell TEM, we herein observed the etching of ceria-based nanocrystals under the control of redox-governing factors. Direct nanoscale observation reveals facet-dependent etching kinetics, thus identifying the specific facet ({100} for reduction and {111} for oxidation) that governs the overall etching under different chemical conditions. Under each redox condition, the contribution of the predominant facet increases as the etching reactivity increases.

Biological Nicotinamide Cofactor as a Redox-Active Motif for Reversible Electrochemical Energy Storage.

Nicotinamide adenine dinucleotide (NAD+ ) is one of the most well-known redox cofactors carrying electrons. Now, it is reported that the intrinsically charged NAD+ motif can serve as an active electrode in electrochemical lithium cells. By anchoring the NAD+ motif by the anion incorporation, redox activity of the NAD+ is successfully implemented in conventional batteries, exhibiting the average voltage of 2.3 V. The operating voltage and capacity are tunable by altering the anchoring anion species without modifying the redox center itself. This work not only demonstrates the redox capability of NAD+ , but also suggests that anchoring the charged molecules with anion incorporation is a viable new approach to exploit various charged biological cofactors in rechargeable battery systems.

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.

In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li+/Na+ substitution during solvothermal ion-exchange synthesis of LixNa1.5-xVOPO4F0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na+ by Li+, leading to peculiar Na+/Li+/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

Large-Scale Synthesis of Carbon-Shell-Coated FeP Nanoparticles for Robust Hydrogen Evolution Reaction Electrocatalyst.

A highly active and stable non-Pt electrocatalyst for hydrogen production has been pursued for a long time as an inexpensive alternative to Pt-based catalysts. Herein, we report a simple and effective approach to prepare high-performance iron phosphide (FeP) nanoparticle electrocatalysts using iron oxide nanoparticles as a precursor. A single-step heating procedure of polydopamine-coated iron oxide nanoparticles leads to both carbonization of polydopamine coating to the carbon shell and phosphidation of iron oxide to FeP, simultaneously. Carbon-shell-coated FeP nanoparticles show a low overpotential of 71 mV at 10 mA cm-2, which is comparable to that of a commercial Pt catalyst, and remarkable long-term durability under acidic conditions for up to 10 000 cycles with negligible activity loss. The effect of carbon shell protection was investigated both theoretically and experimentally. A density functional theory reveals that deterioration of catalytic activity of FeP is caused by surface oxidation. Extended X-ray absorption fine structure analysis combined with electrochemical test shows that carbon shell coating prevents FeP nanoparticles from oxidation, making them highly stable under hydrogen evolution reaction operation conditions. Furthermore, we demonstrate that our synthetic method is suitable for mass production, which is highly desirable for large-scale hydrogen production.

Tin Sulfide-Based Nanohybrid for High-Performance Anode of Sodium-Ion Batteries.

Nanohybrid anode materials for Na-ion batteries (NIBs) based on conversion and/or alloying reactions can provide significantly improved energy and power characteristics, while suffering from low Coulombic efficiency and unfavorable voltage properties. An NIB paper-type nanohybrid anode (PNA) based on tin sulfide nanoparticles and acid-treated multiwalled carbon nanotubes is reported. In 1 m NaPF6 dissolved in diethylene glycol dimethyl ether as an electrolyte, the above PNA shows a high reversible capacity of ≈1200 mAh g-1 and a large voltage plateau corresponding to a capacity of ≈550 mAh g-1 in the low-voltage region of ≈0.1 V versus Na+ /Na, exhibiting high rate capabilities at a current rate of 1 A g-1 and good cycling performance over 250 cycles. In addition, the PNA exhibits a high first Coulombic efficiency of ≈90%, achieving values above 99% during subsequent cycles. Furthermore, the feasibility of PNA usage is demonstrated by full-cell tests with a reported cathode, which results in high specific energy and power values of ≈256 Wh kg-1 and 471 W kg-1 , respectively, with stable cycling.