Impact of Asymmetric Microstructure on Ion Transport in Ti3C2Tx Membranes.

Consolidation or densification of low-dimensional MXene materials into membranes can result in the formation of asymmetric membrane structures. Nanostructural (short-range) and microstructural (long-range) heterogeneity can influence mass transport and separation mechanisms. Short-range structural dynamics include the presence of water confined between the 2D layers, while long-range structural properties include the formation of defects, micropores, and mesopores. Herein, it is demonstrated that structural heterogeneity in Ti3C2Tx membranes fabricated via vacuum-assisted filtration significantly affects ion transport. Higher ion permeabilities are achieved when the dense "bottom" side of the membrane, rather than the porous "top" side, faces the feed solution. Characterization of the membrane reveals distinct differences in flake alignment, surface roughness, and porosity across the membrane. The directional dependence on permeability suggests that one region of the membrane experiences stronger internal concentration polarization, potentially suppressing permeability through the porous side of the membrane.

Silicon Composite Anode Degradation during Freeze-Thaw Temperature-Swings.

Batteries used in space applications can be exposed to large temperature-swings. During these large temperature-swings, the battery electrolyte can undergo a phase transformation from a liquid to a solid and back to a liquid. The nature of the solvent and the type of salt influence the crystallization processes. Herein, we aim to understand how pressure build-up in confined regions of an electrode (e.g., pores) influences degradation processes in silicon-oxide graphite anodes undergoing freeze-thaw dynamics. Our results show that high porosity electrodes lead to a greater density of nucleation sites for electrolyte crystallization. Local pressure build-up at pores results in active material loss and decreased cycle lifetime in batteries exposed to extreme temperature swings.

Ultrasparse View X-ray Computed Tomography for 4D Imaging.

X-ray computed tomography (CT) is a noninvasive, nondestructive approach to imaging materials, material systems, and engineered components in two and three dimensions. Acquisition of three-dimensional (3D) images requires the collection of hundreds or thousands of through-thickness X-ray radiographic images from different angles. Such 3D data acquisition strategies commonly involve suboptimal temporal sampling for in situ and operando studies (4D imaging). Herein, we introduce a sparse-view imaging approach, Tomo-NeRF, which is capable of reconstructing high-fidelity 3D images from <10 two-dimensional radiographic images. Experimental 2D and 3D X-ray images were used to test the reconstruction capability in two-view, four-view, and six-view scenarios. Tomo-NeRF is capable of reconstructing 3D images with a structural similarity of 0.9971-0.9975 and a voxel-wise accuracy of 81.83-89.59% from 2D experimentally obtained images. The reconstruction accuracy for the experimentally obtained images is less than the synthetic structures. Experimentally obtained images demonstrate a similarity of 0.9973-0.9984 and a voxel-wise accuracy of 84.31-95.77%.

Temperature and Pressure Effects on Unrecoverable Voids in Li Metal Solid-State Batteries.

All-solid-state batteries (ASSB) can potentially achieve high gravimetric and volumetric energy densities (900 Wh/L) if paired with a lithium metal anode and solid electrolyte. However, there is a lack in critical understanding about how to operate lithium metal cells at high capacities and minimize unwanted degradation mechanisms such as dendrites and voids. Herein, we investigate how pressure and temperature influence the formation and annihilation of unrecoverable voids in lithium metal upon stripping. Stack pressure and temperature are effective means to initiate creep-induced void filling and decrease charge transfer resistances. Applying stack pressure enables lithium to deform and creep below the yield stress during stripping at high current densities. Lithium creep is not sufficient to prevent cell shorting during plating. Three-electrode experiments were employed to probe the kinetic and morphological limitations that occur at the anode-solid electrolyte during high-capacity stripping (5 mAh/cm2). The role of cathode-LLZO interface, which dictates cyclability and capacity retention in full cells, was also studied. This work elucidates the important role that temperature (external or in situ generated) has on reversible operation of solid-state batteries.

Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics.

Understanding and mitigating filament formation, short-circuit and solid electrolyte fracture is necessary for advanced all-solid-state batteries. Here, we employ a coupled far-field high-energy diffraction microscopy and tomography approach for assessing the chemo-mechanical behaviour for dense, polycrystalline garnet (Li7La3Zr2O12) solid electrolytes with grain-level resolution. In situ monitoring of grain-level stress responses reveals that the failure mechanism is stochastic and affected by local microstructural heterogeneity. Coupling high-energy X-ray diffraction and far-field high-energy diffraction microscopy measurements reveals the presence of phase heterogeneity that can alter local chemo-mechanics within the bulk solid electrolyte. These local regions are proposed to be regions with the presence of a cubic polymorph of LLZO, potentially arising from local dopant concentration variation. The coupled tomography and FF-HEDM experiments are combined with transport and mechanics modelling to illustrate the degradation of polycrystalline garnet solid electrolytes. The results showcase the pathways for processing high-performing solid-state batteries.

In situ investigation of water on MXene interfaces.

A continuum of water populations can exist in nanoscale layered materials, which impacts transport phenomena relevant for separation, adsorption, and charge storage processes. Quantification and direct interrogation of water structure and organization are important in order to design materials with molecular-level control for emerging energy and water applications. Through combining molecular simulations with ambient-pressure X-ray photoelectron spectroscopy, X-ray diffraction, and diffuse reflectance infrared Fourier transform spectroscopy, we directly probe hydration mechanisms at confined and nonconfined regions in nanolayered transition-metal carbide materials. Hydrophobic (K+) cations decrease water mobility within the confined interlayer and accelerate water removal at nonconfined surfaces. Hydrophilic cations (Li+) increase water mobility within the confined interlayer and decrease water-removal rates at nonconfined surfaces. Solutes, rather than the surface terminating groups, are shown to be more impactful on the kinetics of water adsorption and desorption. Calculations from grand canonical molecular dynamics demonstrate that hydrophilic cations (Li+) actively aid in water adsorption at MXene interfaces. In contrast, hydrophobic cations (K+) weakly interact with water, leading to higher degrees of water ordering (orientation) and faster removal at elevated temperatures.

Scalable Manufacturing of Hybrid Solid Electrolytes with Interface Control.

Hybrid solid electrolytes are promising alternatives for high energy density metallic lithium batteries. Scalable manufacturing of multi-material electrolytes with tailored transport pathways can provide an avenue toward controlling Li stripping and deposition mechanisms in all-solid-state devices. A novel roll-to-roll compatible coextrusion device is demonstrated to investigate mesostructural control during manufacturing. Solid electrolytes with 25 and 75 wt % PEO-LLZO compositions are investigated. The coextrusion head is demonstrated to effectively process multimaterial films with strict compositional gradients in a single pass. An average manufacturing variability of 5.75 ± 1.2 µm is observed in the thickness across all the electrolytes manufactured. Coextruded membranes with 1 mm stripes show the highest room temperature conductivity of 8.8 × 10-6 S cm-1 compared to the conductivity of single-material films (25 wt %, 1.2 × 10-6 S cm-1; 75 wt %, 1.8 × 10-6 S cm-1). Distribution of relaxation times and effective mean field theory calculations suggest that the interface generated between the two materials possesses high ion-conducting properties. Computational simulations are used to further substantiate the influence of macroscale interfaces on ion transport.

Tortuosity Effects in Garnet-Type Li7La3Zr2O12 Solid Electrolytes.

Intrinsic material microstructure features, such as pores or void spaces, grains, and defects can affect local lithium-ion concentration profiles and transport properties in solid ion conductors. The formation of lithium-deficient or -excess regions can accelerate degradation phenomena, such as dendrite formation, lithium plating, and electrode/electrolyte delamination. This paper evaluates the effects pores or void spaces have on the tortuosity of a garnet-type Li7La3Zr2O12 solid electrolyte. Synchrotron X-ray tomography is used to obtain three-dimensional reconstructions of different electrolytes sintered at temperatures between 1050 and 1150 °C. The magnitude of the electrolyte tortuosity and the tortuosity directional anisotropy is shown to increase with sintering temperature. Electrolytes with highly anisometric tortuosity have lower critical current densities. Alignment or elimination of pores within an electrolyte or composite cathode may provide a means for achieving higher critical current densities and higher power densities in all solid-state batteries.

The Role of Adventitious Carbon in Photo-catalytic Nitrogen Fixation by Titania.

Photo-catalytic fixation of nitrogen by titania catalysts at ambient conditions has been reported for decades, yet the active site capable of adsorbing an inert N2 molecule at ambient pressure and the mechanism of dissociating the strong dinitrogen triple bond at room temperature remain unknown. In this work in situ near-ambient-pressure X-ray photo-electron spectroscopy and density functional theory calculations are used to probe the active state of the rutile (110) surface. The experimental results indicate that photon-driven interaction of N2 and TiO2 is observed only if adventitious surface carbon is present, and computational results show a remarkably strong interaction between N2 and carbon substitution (C*) sites that act as surface-bound carbon radicals. A carbon-assisted nitrogen reduction mechanism is proposed and shown to be thermodynamically feasible. The findings provide a molecular-scale explanation for the long-standing mystery of photo-catalytic nitrogen fixation on titania. The results suggest that controlling and characterizing carbon-based active sites may provide a route to engineering more efficient photo(electro)-catalysts and improving experimental reproducibility.

Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials.

We report the first examples of purely organic donor-acceptor materials with integrated π-bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne-azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.

Direct observation of active material interactions in flowable electrodes using X-ray tomography.

Understanding electrical percolation and charging mechanisms in electrochemically active biphasic flowable electrodes is critical for enabling scalable deionization (desalination) and energy storage. Flowable electrodes are dynamic material systems which store charge (remove ions) and have the ability to flow. This flow process can induce structural changes in the underlying material arrangement and result in transient and non-uniform material properties. Carbon-based suspensions are opaque, multi-phase, and three dimensional, and thus prior characterization of the structural properties has been limited to indirect methods (electrochemical and rheology). Herein, a range of mixed electronic and ionically conducting suspensions are evaluated to determine their static structure, function, and properties, utilizing synchrotron radiation X-ray tomographic microscopy (SRXTM). The high brilliance of the synchrotron light enables deconvolution of the liquid and solid phases. Reconstruction of the solid phase reveals agglomeration cluster volumes between 10 µm3 and 103µm3 (1 pL) for low loaded samples (5 wt% carbon). The largest agglomeration cluster in the low loaded sample (5 wt%) occupied only 3% of the reconstructed volume whereas samples loaded with 10 wt% activated carbon demonstrated electrically connected clusters that occupied 22% of the imaged region. The highly loaded samples (20 wt%) demonstrated clusters of the order of a microliter, which accounted for 63-85% of the imaged region. These results demonstrate a capability for discerning the structural properties of biphasic systems utilizing SRXTM techniques, and show that discontinuity in the carbon particle networks induces decreased material utilization in low-loaded flowable electrodes.

Materials for suspension (semi-solid) electrodes for energy and water technologies.

Suspension or semi-solid electrodes have recently gained increased attention for large-scale applications such as grid energy storage, capacitive water deionization, and wastewater treatment. A suspension electrode is a multiphase material system comprised of an active (charge storing) material suspended in ionic solution (electrolyte). Gravimetrically, the electrolyte is the majority component and aids in physical transport of the active material. This principle enables, for the first time, scalability of electrochemical energy storage devices (supercapacitors and batteries) previously limited to small and medium scale applications. This critical review describes the ongoing material challenges encompassing suspension-based systems. The research described here combines classical aspects of electrochemistry, colloidal science, material science, fluid mechanics, and rheology to describe ion and charge percolation, adsorption of ions, and redox charge storage processes in suspension electrodes. This review summarizes the growing inventory of material systems, methods and practices used to characterize suspension electrodes, and describes universal material system properties (rheological, electrical, and electrochemical) that are pivotal in the design of high performing systems. A discussion of the primary challenges and future research directions is included.

Effect of oxidation of carbon material on suspension electrodes for flow electrode capacitive deionization.

Flow electrode deionization (FCDI) is an emerging area for continuous and scalable deionization, but the electrochemical and flow properties of the flow electrode need to be improved to minimize energy consumption. Chemical oxidation of granular activated carbon (AC) was examined here to study the role of surface heteroatoms on rheology and electrochemical performance of a flow electrode (carbon slurry) for deionization processes. Moreover, it was demonstrated that higher mass densities could be used without increasing energy for pumping when using oxidized active material. High mass-loaded flow electrodes (28% carbon content) based on oxidized AC displayed similar viscosities (∼21 Pa s) to lower mass-loaded flow electrodes (20% carbon content) based on nonoxidized AC. The 40% increased mass loading (from 20% to 28%) resulted in a 25% increase in flow electrode gravimetric capacitance (from 65 to 83 F g(-1)) without sacrificing flowability (viscosity). The electrical energy required to remove ∼18% of the ions (desalt) from of the feed solution was observed to be significantly dependent on the mass loading and decreased (∼60%) from 92 ± 7 to 28 ± 2.7 J with increased mass densities from 5 to 23 wt %. It is shown that the surface chemistry of the active material in a flow electrode effects the electrical and pumping energy requirements of a FCDI system.

Charge- and Size-Selective Ion Sieving Through Ti3C2Tx MXene Membranes.

Nanometer-thin sheets of 2D Ti3C2Tx (MXene) have been assembled into freestanding or supported membranes for the charge- and size-selective rejection of ions and molecules. MXene membranes with controllable thicknesses ranging from hundreds of nanometers to several micrometers exhibited flexibility, high mechanical strength, hydrophilic surfaces, and electrical conductivity that render them promising for separation applications. Micrometer-thick MXene membranes demonstrated ultrafast water flux of 37.4 L/(Bar·h·m(2)) and differential sieving of salts depending on both the hydration radius and charge of the ions. Cations with a larger charge and hydration radii smaller than the interlayer spacing of MXene (∼6 Å) demonstrate an order of magnitude slower permeation compared to single-charged cations. Our findings may open a door for developing efficient and highly selective separation membranes from 2D carbides.

Composite manganese oxide percolating networks as a suspension electrode for an asymmetric flow capacitor.

In this study, we examine the use of a percolating network of metal oxide (MnO2) as the active material in a suspension electrode as a way to increase the capacitance and energy density of an electrochemical flow capacitor. Amorphous manganese oxide was synthesized via a low-temperature hydrothermal approach and combined with carbon black to form composite flowable electrodes of different compositions. All suspension electrodes were tested in static configurations and consisted of an active solid material (MnO2 or activated carbon) immersed in aqueous neutral electrolyte (1 M Na2SO4). Increasing concentrations of carbon black led to better rate performance but at the cost of capacitance and viscosity. Furthermore, it was shown that an expanded voltage window of 1.6 V could be achieved when combining a composite MnO2-carbon black (cathode) and an activated carbon suspension (anode) in a charge balanced asymmetric device. The expansion of the voltage window led to a significant increase in the energy density to ∼11 Wh kg(-1) at a power density of ∼50 W kg(-1). These values are ∼3.5 times and ∼2 times better than a symmetric suspension electrode based on activated carbon.