High-Entropy Spinel Oxide Ferrites for Battery Applications.

Four different high-entropy spinel oxide ferrite (HESO) electrode materials containing 5-6 distinct metals were synthesized by a simple, rapid combustion synthesis process and evaluated as conversion anode materials in lithium half-cells. All showed markedly superior electrochemical performance compared to conventional spinel ferrites such as Fe3O4 and MgFe2O4, having capacities that could be maintained above 600 mAh g-1 for 150 cycles, in most cases. X-ray absorption spectroscopy (XAS) results on pristine, discharged, and charged electrodes show that Fe, Co, Ni, and Cu are reduced to the elemental state during the first discharge (lithiation), while Mn is only slightly reduced. Upon recharge (delithiation), Fe is reoxidized to an average oxidation state of about 2.6+, while Co, Ni, and Cu are not reoxidized. The ability of Fe to be oxidized past 2+ accounts for the high capacities observed in these materials, while the presence of metallic elements after the initial lithiation provides an electronically conductive network that aids in charge transfer.

Assembled MXene-Liquid Metal Cages on Silicon Microparticles as Self-Healing Battery Anodes.

In pursuit of higher energy density in lithium-ion batteries, silicon (Si) has been recognized as a promising candidate to replace commercial graphite due to its high theoretical capacity. However, the pulverization issue of Si microparticles during lithiation/delithiation results in electrical contact loss and increased side reactions, significantly limiting its practical applications. Herein, we propose to utilize liquid metal (LM) particles as the bridging agent, which assemble conductive MXene (Ti3C2Tx) sheets via coordination chemistry, forming cage-like structures encapsulating mSi particles as self-healing high-energy anodes. Due to the integration of robust Ti3C2Tx sheets and deformable LM particles as conductive buffering cages, simultaneously high-rate capability and cyclability can be realized. Post-mortem analysis revealed the cage structural integrity and the maintained electrical percolating network after cycling. This work introduces an effective approach to accommodate structural change via a resilient encapsulating cage and offers useful interface design considerations for versatile battery electrodes.

Kinetic trapping of nanoparticles by solvent-induced interactions.

Theoretical analysis based on mean field theory indicates that solvent-induced interactions (i.e. structural forces due to the rearrangement of wetting solvent molecules) not considered in DLVO theory can induce the kinetic trapping of nanoparticles at finite nanoscale separations from a well-wetted surface, under a range of ubiquitous physicochemical conditions for inorganic nanoparticles of common materials (e.g., metal oxides) in water or simple molecular solvents. This work proposes a simple analytical model that is applicable to arbitrary materials and simple solvents to determine the conditions for direct particle-surface contact or kinetic trapping at finite separations, by using experimentally measurable properties (e.g., Hamaker constants, interfacial free energies, and nanoparticle size) as input parameters. Analytical predictions of the proposed model are verified by molecular dynamics simulations and numerical solution of the Smoluchowski diffusion equation.

Fast-Charging, Binder-Free Lithium Battery Cathodes Enabled via Multidimensional Conductive Networks.

To meet the growing demands in both energy and power densities of lithium ion batteries, electrode structures must be capable of facile electron and ion transport while minimizing the content of electrochemically inactive components. Herein, binder-free LiFePO4 (LFP) cathodes are fabricated with a multidimensional conductive architecture that allows for fast-charging capability, reaching a specific capacity of 94 mAh g-1 at 4 C. Such multidimensional networks consist of active material particles wrapped by 1D single-walled carbon nanotubes (CNTs) and bound together using 2D MXene (Ti3C2Tx) nanosheets. The CNTs form a porous coating layer and improve local electron transport across the LFP surface, while the Ti3C2Tx nanosheets provide simultaneously high electrode integrity and conductive pathways through the bulk of the electrode. This work highlights the ability of multidimensional conductive fillers to realize simultaneously superior electrochemical and mechanical properties, providing useful insights into future fast-charging electrode designs for scalable electrochemical systems.

Enhancing composite electrode performance: insights into interfacial interactions.

Propelled by the widespread adoption of portable electronic devices, electrochemical energy storage systems, particularly lithium-ion batteries (LIBs), have become ubiquitous in modern society. The electrode is the critical battery component, where intricate interactions between the materials govern both the energy output and the overall lifespan of the battery under operational conditions. However, the poor interfacial properties of traditional electrode materials fall short in meeting escalating performance demands. To facilitate the advent of next-generation lithium-ion batteries, attention must be devoted to the interfacial chemistry that dictates and modulates the various dynamic and transport processes across multiple length scales within the composite electrodes. Recent research has concentrated on systematically understanding the properties of distinct electrode components to engineer meticulously tailored electrode formulations. These are geared towards composite electrodes with heightened chemical stability, thermal robustness, enhanced local conductivities, and superior mechanical resilience. This review elucidates the latest advances in understanding the impact of interfacial interactions in achieving high-capacity, high-stability electrodes. Through comprehensive insights into the interfacial interactions between the various electrode components, we can create improved integrated systems that outperform those developed through empirical methods. In light of this, the adoption of a holistic approach to enhance the interactions among electrode materials becomes of paramount importance. This concerted effort ensures the attainment of heightened rate capability, facilitation of lithium-ion transport, and overall system stability throughout the entirety of the cyclic process.

Mechanism of Chalcophanite Nucleation in Zinc Hydroxide Sulfate Cathodes in Aqueous Zinc Batteries.

Aqueous Zn-ion batteries with MnO2-based cathodes have seen significant attention owing to their high theoretical capacities, safety, and low cost; however, much debate remains regarding the reaction mechanism that dominates energy storage. In this work, we report our electron microscopy study of cathodes containing zinc hydroxide sulfate (Zn4SO4(OH)6·xH2O, ZHS) together with carbon nanotubes cycled in electrolytes containing ZnSO4 with varied amounts of MnSO4 incorporated. The primary Mn-containing phase is formed in situ in the cathode during cycling, where a dissolution-deposition reaction is identified between ZHS and chalcophanite (ZnMn3O7·3H2O). Mechanistic details of this reaction, in which the chalcophanite nucleates then separates from the ZHS flakes as the ZHS dissolves while acting as the primary Zn source for the reaction, are revealed using surface sensitive methods. These findings indicate the reaction is local to the ZHS flakes, providing new insight toward the importance of ZHS and the cathode microstructure.

The Relationship between Ionic Conductivity and Solvation Structures of Localized High-Concentration Fluorinated Electrolytes for Lithium-Ion Batteries.

Localized high-concentration electrolytes (LHCEs) combine a diluent with a high-concentration electrolyte, offering promising properties. The ions, solvent, and diluent interact to form complex heterogeneous liquid structures, where high salt concentration clusters are embedded in the diluent. Optimizing LHCEs for desired electrolyte properties like high ionic conductivity, low viscosity, and effective solid electrolyte interphase (SEI) formation ability within the vast chemical and compositional design space requires deeper understanding and theoretical guidance. We investigated the structures and conductivities of LHCEs based on a fluorinated solvent with two different diluents at varying concentrations. 2,2,3,3-Tetrafluoropropyl trifluoroacetate (TFPTFA) enters the solvation cluster due to its stronger Li-ion interactions, whereas 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFETFE) enters only at extremely high diluent concentrations. The ionic conductivity increases with decreasing diluent concentrations, with a slope change during cluster percolation. Overall, TFETFE demonstrates higher effectiveness than TFPTFA, forming higher local salt concentration clusters and resulting in higher ionic conductivity.

Densified vertically lamellar electrode architectures for compact energy storage.

As one of the most compact electrochemical energy storage systems, lithium-ion batteries (LIBs) are playing an indispensable role in the process of vehicle electrification to accelerate the shift to sustainable mobility. Making battery electrodes thicker is a promising strategy for improving the energy density of LIBs which is essential for applications with weight or volume constraints, such as electric-powered transportation; however, their power densities are often significantly restricted due to elongated and tortuous charge traveling distances. Here, we propose an effective methodology that couples bidirectional freeze-casting and compression-induced densification to create densified vertically lamellar electrode architectures for compact energy storage. The vertically lamellar architectures not only overcome the critical thickness limit for conventional electrodes but also facilitate and redistribute the lithium-ion flux enabling both high rate capability and stable cyclability. Furthermore, this proposed methodology is universal as demonstrated in various electrochemical active material systems. This study offers a facile approach that realizes simultaneous high energy and high power in high-loading battery electrodes and provides useful rationales in designing electrode architectures for scalable energy storage systems.

Microwave-Assisted Fabrication of High Energy Density Binary Metal Sulfides for Enhanced Performance in Battery Applications.

Nanomaterials have found use in a number of relevant energy applications. In particular, nanoscale motifs of binary metal sulfides can function as conversion materials, similar to that of analogous metal oxides, nitrides, or phosphides, and are characterized by their high theoretical capacity and correspondingly low cost. This review focuses on structure-composition-property relationships of specific relevance to battery applications, emanating from systematic attempts to either (1) vary and alter the dimension of nanoscale architectures or (2) introduce conductive carbon-based entities, such as carbon nanotubes and graphene-derived species. In this study, we will primarily concern ourselves with probing metal sulfide nanostructures generated by a microwave-mediated synthetic approach, which we have explored extensively in recent years. This particular fabrication protocol represents a relatively facile, flexible, and effective means with which to simultaneously control both chemical composition and physical morphology within these systems to tailor them for energy storage applications.

Two-Dimensional Siloxene Nanosheets: Impact of Morphology and Purity on Electrochemistry.

Two-dimensional (2D) siloxene (Si6O3H6) has shown promise as a negative electrode material for Li-ion batteries due to its high gravimetric capacity and superior mechanical properties under (de)lithiation compared to bulk Si. In this work, we prepare purified siloxene nanosheets through the removal of bulk Si contaminants, use ultrasonication to control the lateral size and thickness of the nanosheets, and probe the effects of the resulting morphology and purity on the electrochemistry. The thin siloxene nanosheets formed after 4 h of ultrasonication deliver an average capacity of 810 mA h/g under a 1000 mA/g rate over 200 cycles with a capacity retention of 76%. Interestingly, the purified siloxene shows lower initial capacity but superior capacity retention over extended cycling. The 2D morphology benefit is illustrated where the parent siloxene nanosheet morphology and structure were largely maintained based on operando optoelectrochemistry, in situ Raman, ex situ scanning electron microscopy, and ex situ transmission electron microscopy. Furthermore, the purified siloxene-based electrode free from crystalline Si impurity experiences the least expansion upon (de)lithiation as visualized by cross-section electron microscopy of samples recovered post-cycling.

Spatiotemporal Resolution of Phase Formation in Thick Porous Sodium Vanadium Oxide (NaV3O8) Electrodes via Operando Energy Dispersive X-ray Diffraction.

Herein, zinc vanadium oxide (ZVO) and zinc hydroxy-sulfate (ZHS) formation as discharge products in sodium vanadium oxide (NVO) cathode materials of two distinct morphologies, NVO(300) and NVO(500), is studied with ex situ and operando X-ray diffraction methods. ZHS formation upon discharge is shown to be favored at higher current densities and reversible upon charge, while ZVO formation is found to be favored at lower current densities but persists throughout cycling. Operando synchrotron-based energy dispersive X-ray diffraction (EDXRD) reveals reversible expansion of the NVO lattice due to Zn2+ during discharge, spontaneous ZVO formation following cell assembly, and ZHS formation concomitant with H+ insertion at potentials less than ∼0.8 V vs Zn/Zn2+. With spatially resolved EDXRD, ZVO formation is show to occur near the separator region first, eventually moving to the current collector region as discharge depth increases. ZHS formation, however, is found to originate from the current collector side of the positive electrode and then propagate through the porous electrode network. This study highlights the special benefits of the EDXRD method to gain mechanistic insight into structural evolution within the electrode and at its interface.

Electron and Ion Transport in Lithium and Lithium-Ion Battery Negative and Positive Composite Electrodes.

Electrochemical energy storage systems, specifically lithium and lithium-ion batteries, are ubiquitous in contemporary society with the widespread deployment of portable electronic devices. Emerging storage applications such as integration of renewable energy generation and expanded adoption of electric vehicles present an array of functional demands. Critical to battery function are electron and ion transport as they determine the energy output of the battery under application conditions and what portion of the total energy contained in the battery can be utilized. This review considers electron and ion transport processes for active materials as well as positive and negative composite electrodes. Length and time scales over many orders of magnitude are relevant ranging from atomic arrangements of materials and short times for electron conduction to large format batteries and many years of operation. Characterization over this diversity of scales demands multiple methods to obtain a complete view of the transport processes involved. In addition, we offer a perspective on strategies for enabling rational design of electrodes, the role of continuum modeling, and the fundamental science needed for continued advancement of electrochemical energy storage systems with improved energy density, power, and lifetime.

Simultaneous Elucidation of Solid and Solution Manganese Environments via Multiphase Operando Extended X-ray Absorption Fine Structure Spectroscopy in Aqueous Zn/MnO2 Batteries.

Aqueous Zn/MnO2 batteries (AZMOB) with mildly acidic electrolytes hold promise as potential green grid-level energy storage solutions for clean power generation. Mechanistic understanding is critical to advance capacity retention needed by the application but is complex due to the evolution of the cathode solid phases and the presence of dissolved manganese in the electrolyte due to a dissolution-deposition redox process. This work introduces operando multiphase extended X-ray absorption fine structure (EXAFS) analysis enabling simultaneous characterization of both aqueous and solid phases involved in the Mn redox reactions. The methodology was successfully conducted in multiple electrolytes (ZnSO4, Zn(CF3SO3)2, and Zn(CH3COO)2) revealing similar manganese coordination environments but quantitative differences in distribution of Mnn+ species in the solid and solution phases. Complementary Raman spectroscopy was utilized to identify the less crystalline Mn-containing products formed under charge at the cathodes. This was further augmented by transmission electron microscopy (TEM) to reveal the morphology and surface condition of the deposited solids. The results demonstrate an effective approach for bulk-level characterization of poorly crystalline multiphase solids while simultaneously gaining insight into the dissolved transition-metal species in solution. This work provides demonstration of a useful approach toward gaining insight into complex electrochemical mechanisms where both solid state and dissolved active materials are important contributors to redox activity.

Design principles for heterointerfacial alloying kinetics at metallic anodes in rechargeable batteries.

How surface chemistry influences reactions occurring thereupon has been a long-standing question of broad scientific and technological interest. Here, we consider the relation between the surface chemistry at interfaces and the reversibility of electrochemical transformations at rechargeable battery electrodes. Using Zn as a model system, we report that a moderate strength of chemical interaction between the deposit and the substrate-neither too weak nor too strong-enables highest reversibility and stability of the plating/stripping redox processes. Focused ion beam and electron microscopy were used to directly probe the morphology, chemistry, and crystallography of heterointerfaces of distinct natures. Analogous to the empirical Sabatier principle for chemical heterogeneous catalysis, our findings arise from competing interfacial processes. Using full batteries with stringent negative electrode-to-positive electrode capacity (N:P) ratios, we show that such knowledge provides a powerful tool for designing key materials in highly reversible battery systems based on Earth-abundant, low-cost metals such as Zn and Na.

Vertically assembled nanosheet networks for high-density thick battery electrodes.

As one of the prevailing energy storage systems, lithium-ion batteries (LIBs) have become an essential pillar in electric vehicles (EVs) during the past decade, contributing significantly to a carbon-neutral future. However, the complete transition to electric vehicles requires LIBs with yet higher energy and power densities. Here, we propose an effective methodology via controlled nanosheet self-assembly to prepare low-tortuosity yet high-density and high-toughness thick electrodes. By introducing a delicate densification in a three-dimensionally interconnected nanosheet network to maintain its vertical architecture, facile electron and ion transports are enabled despite their high packing density. This dense and thick electrode is capable of delivering a high volumetric capacity >1,600 mAh cm-3, with an areal capacity up to 32 mAh cm-2, which is among the best reported in the literature. The high-performance electrodes with superior mechanical and electrochemical properties demonstrated in this work provide a potentially universal methodology in designing advanced battery electrodes with versatile anisotropic properties.

Tortuosity Engineering for Improved Charge Storage Kinetics in High-Areal-Capacity Battery Electrodes.

The increasing demands of electronic devices and electric transportation necessitate lithium-ion batteries with simultaneous high energy and power capabilities. However, rate capabilities are often limited in high-loading electrodes due to the lengthy and tortuous ion transport paths with their electrochemical behaviors governed by complicated electrode architectures still elusive. Here, we report the electrode-level tortuosity engineering design enabling improved charge storage kinetics in high-energy electrodes. Both high areal capacity and high-rate capability can be achieved beyond the practical level of mass loadings in electrodes with vertically oriented architectures. The electrochemical properties in electrodes with various architectures were quantitatively investigated through correlating the characteristic time with tortuosity. The lithium-ion transport kinetics regulated by electrode architectures was further studied via combining the three-dimensional electrode architecture visualization and simulation. The tortuosity-controlled charge storage kinetics revealed in this study can be extended to general electrode systems and provide useful design consideration for next-generation high-energy/power batteries.

Gradient Design for High-Energy and High-Power Batteries.

Charge transport is a key process that dominates battery performance, and the microstructures of the cathode, anode, and electrolyte play a central role in guiding ion and/or electron transport inside the battery. Rational design of key battery components with varying microstructure along the charge-transport direction to realize optimal local charge-transport dynamics can compensate for reaction polarization, which accelerates electrochemical reaction kinetics. Here, the principles of charge-transport mechanisms and their decisive role in battery performance are presented, followed by a discussion of the correlation between charge-transport regulation and battery microstructure design. The design strategies of the gradient cathodes, lithium-metal anodes, and solid-state electrolytes are summarized. Future directions and perspectives of gradient design are provided at the end to enable practically accessible high-energy and high-power-density batteries.

The Dopamine Assisted Synthesis of MoO3/Carbon Electrodes With Enhanced Capacitance in Aqueous Electrolyte.

A capacitance increase phenomenon is observed for MoO3 electrodes synthesized via a sol-gel process in the presence of dopamine hydrochloride (Dopa HCl) as compared to α-MoO3 electrodes in 5M ZnCl2 aqueous electrolyte. The synthesis approach is based on a hydrogen peroxide-initiated sol-gel reaction to which the Dopa HCl is added. The powder precursor (Dopa)xMoOy, is isolated from the metastable gel using freeze-drying. Hydrothermal treatment (HT) of the precursor results in the formation of MoO3 accompanied by carbonization of the organic molecules; designated as HT-MoO3/C. HT of the precipitate formed in the absence of dopamine in the reaction produced α-MoO3, which was used as a reference material in this study (α-MoO3-ref). Scanning electron microscopy (SEM) images show a nanobelt morphology for both HT-MoO3/C and α-MoO3-ref powders, but with distinct differences in the shape of the nanobelts. The presence of carbonaceous content in the structure of HT-MoO3/C is confirmed by FTIR and Raman spectroscopy measurements. X-ray diffraction (XRD) and Rietveld refinement analysis demonstrate the presence of α-MoO3 and h-MoO3 phases in the structure of HT-MoO3/C. The increased specific capacitance delivered by the HT-MoO3/C electrode as compared to the α-MoO3-ref electrode in 5M ZnCl2 electrolyte in a -0.25-0.70 V vs. Ag/AgCl potential window triggered a more detailed study in an expanded potential window. In the 5M ZnCl2 electrolyte at a scan rate of 2 mV s-1, the HT-MoO3/C electrode shows a second cycle capacitance of 347.6 F g-1. The higher electrochemical performance of the HT-MoO3/C electrode can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Our study provides a new route for further development of metal oxides for energy storage applications.

Multimodal electrochemistry coupled microcalorimetric and X-ray probing of the capacity fade mechanisms of Nickel rich NMC - progress and outlook.

Lithium nickel manganese cobalt oxide (NMC) is a commercially successful Li-ion battery cathode due to its high energy density; however, its delivered capacity must be intentionally limited to achieve capacity retention over extended cycling. To design next-generation NMC batteries with longer life and higher capacity the origins of high potential capacity fade must be understood. Operando hard X-ray characterization techniques are critical for this endeavor as they allow the acquisition of information about the evolution of structure, oxidation state, and coordination environment of NMC as the material (de)lithiates in a functional battery. This perspective outlines recent developments in the elucidation of capacity fade mechanisms in NMC through hard X-ray probes, surface sensitive soft X-ray characterization, and isothermal microcalorimetry. A case study on the effect of charging potential on NMC811 over extended cycling is presented to illustrate the benefits of these approaches. The results showed that charging to 4.7 V leads to higher delivered capacity, but much greater fade as compared to charging to 4.3 V. Operando XRD and SEM results indicated that particle fracture from increased structural distortions at >4.3 V was a contributor to capacity fade. Operando hard XAS revealed significant Ni and Co redox during cycling as well as a Jahn-Teller distortion at the discharged state (Ni3+); however, minimal differences were observed between the cells charged to 4.3 and 4.7 V. Additional XAS analyses using soft X-rays revealed significant surface reconstruction after cycling to 4.7 V, revealing another contribution to fade. Operando isothermal microcalorimetry (IMC) indicated that the high voltage charge to 4.7 V resulted in a doubling of the heat dissipation when compared to charging to 4.3 V. A lowered chemical-to-electrical energy conversion efficiency due to thermal energy waste was observed, providing a complementary characterization of electrochemical degradation. The work demonstrates the utility of multi-modal X-ray and microcalorimetric approaches to understand the causes of capacity fade in lithium-ion batteries with Ni-rich NMC.

Gradient Architecture Design in Scalable Porous Battery Electrodes.

Because it has been demonstrated to be effective toward faster ion diffusion inside the pore space, low-tortuosity porous architecture has become the focus in thick electrode designs, and other possibilities are rarely investigated. To advance current understanding in the structure-affected electrochemistry and to broaden horizons for thick electrode designs, we present a gradient electrode design, where porous channels are vertically aligned with smaller openings on one end and larger openings on the other. With its 3D morphology carefully visualized by Raman mapping, the electrochemical properties between opposite orientations of the gradient electrodes are compared, and faster energy storage kinetics is found in larger openings and more concentrated active material near the separator. As further verified by simulation, this study on gradient electrode design deepens the knowledge of structure-related electrochemistry and brings perspectives in high-energy battery electrode designs.