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This perspective article describes the use of energy dispersive X-ray diffraction (EDXRD) to study the evolution of electrochemical energy storage materials. Using a synchrotron light source, EDXRD allows crystallographic changes in materials to be tracked from deep within large specimens, due to the use of highly penetrating X-rays and the ability to define a well-controlled diffraction gauge volume in space. Herein we provide an overview of battery work performed using the EDXRD technique, as developed at beamline X17B1 at the National Synchrotron Light Source (NSLS), and continued at beamline 6BM-A at the Advanced Photon Source (APS), beamline I12 at the Diamond Light Source, and beamline 7T-MPW-EDDI at the Berlin Electron Storage Ring Society for Synchrotron Radiation (BESSY II). The High Energy Engineering X-Ray Scattering (HEX) beamline currently under construction at the National Synchrotron Light Source II (NSLS-II) by Brookhaven National Lab and the State of New York will further expand capability for and access to this technique. The article begins with a general introduction to the technique of EDXRD, including a description of the photon energy and d-spacing relationship and a discussion of the gauge volume. The primary topic of the review, battery characterization by EDXRD, includes discussion of batteries of differing materials chemistries (lithium-based batteries and aqueous batteries) which store energy by different mechanisms (insertion and conversion materials). A discussion of high temperature batteries is also included.

One of the inherent challenges with Li-S batteries is polysulfide dissolution, in which soluble polysulfide species can contribute to the active material loss from the cathode and undergo shuttling reactions inhibiting the ability to effectively charge the battery. Prior theoretical studies have proposed the possible benefit of defective 2 D MoS2 materials as polysulfide trapping agents. Herein the synthesis and thorough characterization of hydrothermally prepared MoS2 nanosheets that vary in layer number, morphology, lateral size, and defect content are reported. The materials were incorporated into composite sulfur-based cathodes and studied in Li-S batteries with environmentally benign ether-based electrolytes. Through directed synthesis of the MoS2 additive, the relationship between synthetically induced defects in 2 D MoS2 materials and resultant electrochemistry was elucidated and described.

Molybdenum(IV) sulfide (MoS2) has generated significant interest as an electroactive material for Li-ion batteries because of its high theoretical capacity, good rate capability, and minimal volume...

Solid state batteries are an emerging alternative to traditional liquid electrolyte cells that provide potential for safe and high-energy density power sources. This report describes a self-forming, solid state battery based on the Li/I2 couple using an LiI-rich LiI(3-hydroxypropionitrile)2 electrolyte (LiI–LiI(HPN)2). As the negative and positive active materials are generated in situ, the solid electrolyte–current collector interfaces play a critical role in determining the electrochemical response of the battery. Herein, we report the investigation of solid electrolyte–current collector interfaces with a self-forming LiI–LiI(HPN)2 solid electrolyte and the role of varying interface design in reducing resistance during cycling.

Fe3O4 nanoparticles (NPs) with an average size of 8-10 nm have been successfully functionalized with various surface-treatment agents to serve as model systems for probing surface chemistry-dependent electrochemistry of the resulting electrodes. The surface-treatment agents used for the functionalization of Fe3O4 anode materials were systematically varied to include aromatic or aliphatic structures: 4-mercaptobenzoic acid, benzoic acid (BA), 3-mercaptopropionic acid, and propionic acid (PA). Both structural and electrochemical characterizations have been used to systematically correlate the electrode functionality with the corresponding surface chemistry. Surface treatment with ligands led to better Fe3O4 dispersion, especially with the aromatic ligands. Electrochemistry was impacted where the PA- and BA-treated Fe3O4 systems without the -SH group demonstrated a higher rate capability than their thiol-containing counterparts and the pristine Fe3O4. Specifically, the PA system delivered the highest capacity and cycling stability among all samples tested. Notably, the aromatic BA system outperformed the aliphatic PA counterpart during extended cycling under high current density, due to the improved charge transfer and ion transport kinetics as well as better dispersion of Fe3O4 NPs, induced by the conjugated system. Our surface engineering of the Fe3O4 electrode presented herein, highlights the importance of modifying the structure and chemistry of surface-treatment agents as a plausible means of enhancing the interfacial charge transfer within metal oxide composite electrodes without hampering the resulting tap density of the resulting electrode.

While lithium sulfur batteries (Li–S) hold promise as future high energy density low cost energy storage systems, barriers to implementation include low sulfur loading, limited cycle life, and the use of toxic electrolyte solvents. A comprehensive study of Li–S cells in the environmentally benign di(propylene glycol) dimethyl ether (DPGDME)-based electrolyte, using as-prepared MoS2 nanosheets derived from a facile aqueous microwave synthesis as polysulfide trapping agents, is reported herein for the first time. Conventional coated foil electrodes and binder-free electrodes (BFEs) with various structures are systematically generated and tested to correlate electrode design with the resulting electrochemical behavior. Significantly improved Li–S electrochemistry is demonstrated through the synergy of MoS2 chemistry and binder-free electrode engineering. In the coating configuration, the MoS2-containing cell evinced better rate performance and more stable cyclability than the cell without MoS2. In comparison...

This study demonstrates that thermal regeneration is an effective approach to convert degraded phases to functioning electroactive materials, restore functional delivered capacity and recover material crystallinity while retaining the integrity of the parent electrode. V2O5 nanowires were synthesized through a facile hydrothermal method and used to fabricate V2O5/carbon nanotube (CNT) binder free electrodes. Discharge of the V2O5–CNT electrodes coupled with operando energy dispersive X-ray diffraction shows no evidence of phase segregation throughout the 150 μm thick binder free electrodes indicating full utilization of a thick electrode. When V2O5 is highly electrochemically lithiated (x > 2 in LixV2O5), irreversible phase transformation to ω-LixV2O5 was observed, accompanied by a capacity decrease of ∼40% over 100 cycles. A simple thermal treatment of the entire electrode results in a delivered capacity equal to or higher than the original value. Both phase conversion and an increase in material crystallinity as a result of thermal treatment are observed where structural analysis indicates the formation of Li1V3O8. The electrode design approach with thick electrodes and functional thermal regeneration may provide a broader choice of electroactive materials through decreasing the environmental burden by extending the lifetime of energy storage systems.

Vanadium dioxides exist as a variety of polymorphs, each with differing structural and electrochemical capabilities. The monoclinic to rutile transition is an interesting system for study as the transition temperature is easily accessible at moderate temperature and corresponds to an increase in electrical conductivity by 2 orders of magnitude. The transition from monoclinic to rutile is characterized structurally herein using synchrotron-based X-ray diffraction and related to lithium-ion electrochemistry using electrochemical impedance spectroscopy and intermittent pulsatile galvanostatic discharge tests. The experimental results indicate a decrease in ohmic resistance for lithium-based cells tested under higher temperatures. Complementary density functional theory calculations described the experimentally measured intercalation voltages and identified a possible Li-induced LixVO2(M) to LixVO2(R) phase transition during the discharging process rationalizing the favorable impact on the function of a lithi...

ConspectusFuture advances in energy storage systems rely on identification of appropriate target materials and deliberate synthesis of the target materials with control of their physiochemical properties in order to disentangle the contributions of distinct properties to the functional electrochemistry. This goal demands systematic inquiry using model materials that provide the opportunity for significant synthetic versatility and control. Ideally, a material family that enables direct manipulation of characteristics including composition, defects, and crystallite size while remaining within the defined structural framework would be necessary. Accomplishing this through direct synthetic methods is desirable to minimize the complicating effects of secondary processing.The structural motif most frequently used for insertion type electrodes is based on layered type structures where ion diffusion in two dimensions can be envisioned. However, lattice expansion and contraction associated with the ion movement a...

In battery systems, a solid electrolyte interphase (SEI) is formed through electrolyte reaction on an electrode surface. The formation of SEI can have both positive and negative effects on electrochemistry. The initial formation of the layer protects the electrode from further reactivity, which can improve both shelf and cycle life. However, if the layer continues to form, it can impede charge transfer, which increases cell resistance and limits cycle life. The role of SEI is particularly important when studying conversion electrodes, since phase transformations which unveil new electroactive surfaces during reduction/oxidation can facilitate electrolyte decomposition. This manuscript highlights recent developments in the understanding and control of SEI formation for magnetite (Fe3O4) conversion electrodes through electrolyte and electrode modification.

It is both challenging and desirable to have drug sensitizers released at acidic tumor pH for photodynamic therapy in cancer treatment. A pH-responsive carrier was prepared, in which fumed silica-attached 5,10,15,20-tetrakis(4-trimethylammoniophenyl)porphyrin (TTMAPP) was encapsulated into 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) nanocomposite liposomes. The sizes of agglomerates were determined by dynamic light scattering to be 115 nm for silica and 295 nm for silica-TTMAPP-DOPC liposomes. Morphological changes were also found in TEM images, showing liposome formation at pH 8.5 but collapse upon silanol protonation. TTMAPP release is enhanced from 13% at pH 7.5 to 80% at pH 2.3, as determined spectrophotometrically through dialysis membranes. Fluorescence emission of TTMAPP encapsulated in the dry film of liposomes was reduced to half at pH 8.6 when compared to that at pH 5.4, while the production of singlet oxygen was quintupled at pH 5.0 compared to pH 7.6. Upon treatment of human prostate cancer cells with liposomes containing 6.7 μM, 13 μM, 17 μM and 20 μM TTMAPP, the cell viabilities were determined to be 60%, 18%, 20% and 5% at pH 5.4; 58%, 30%, 25% and 10% at pH 6.3; and 90%, 82%, 68% and 35% at pH 7.4, respectively. Light-induced apoptosis in cancerous cells was only observed in the presence of liposomes at pH 6.3 and pH 5.4 but not at pH 7.4, as indicated by chromatin condensation.

One of the inherent challenges with Li-S batteries is polysulfide dissolution, in which soluble polysulfide species can contribute to the active material loss from the cathode and undergo shuttling reactions inhibiting the ability to effectively charge the battery. Prior theoretical studies have proposed the possible benefit of defective 2 D MoS

Actinium-225 (225Ac) can be produced from a Thorium-229/Radium-225 (229Th/225Ra) generator, from high/low energy proton irradiated natural Thorium or Radium-226 target. Titanium based ion exchanger were evaluated for purification of 225Ac. Poorly crystalline silicotitanate (PCST) ion exchanger had high selectivity for Ba, Ag and Th. 225Ac was received with trace amounts of 227Ac, 227Th and 223Ra, and the solution was used to evaluate the retention of the isotopes on PCST ion exchanger. Over 90% of the 225Ac was recovered from PCST, and the radiopurity was >99% (calculated based on 225Ac, 227Th, and 223Ra). The capacity of the PCST inorganic ion exchange for Barium and 232Th was determined to be 24.19 mg/mL for Barium and 5.05 mg/mL for Thorium. PCST ion exchanger could separate 225Ac from isotopes of Ra and Th, and the process represents an interesting one step separation that could be used in an 225Ac generator from 225Ra and/or 229Th. Capacity studies indicated PCST could be used to separate 225Ac produced on small 226Ra targets (0.3–1 g), but PCST did not have a high enough capacity for production scale Th targets (50–100 g).

Fe

Vanadium dioxides exist as different polymorphs, each with unique electrochemical properties. Herein, we investigate the monoclinic to rutile transition of vanadium dioxide using different temperatures. The transition from monoclinic to rutile is characterized using synchrotron-based X-ray diffraction and electrochemical performance is performed using electrochemical impedance spectroscopy and intermittent pulsatile galvanostatic discharge tests in a lithium-ion environment. The experimental results indicate a decrease in ohmic resistance when lithium-ion cells are tested at higher temperatures. Density functional theory calculations also identified a possible LixVO2(M) to LixVO2(R) phase transition during the discharging process. Since the monoclinic to rutile transition corresponds to an increase of electrical conductivity by 2 orders of magnitude this can favorably impact the function of a lithium-based electrochemical cell.

Solid state electrolytes are receiving significant interest due to the prospect of improved safety, however, addressing the incidence and consequence of internal short circuits remains an important issue. Herein, a battery based on a LiI-LiI(HPN)2 solid state electrolyte demonstrated self-healing after internal shorting where the cells recovered and continued to cycle effectively. The functional rechargeable electrochemistry of the self-forming Li/I2-based battery was investigated through interfacial modification by inclusion of Li metal (at the negative interface), and/or fabricated carbon nanotube substrates at the positive interface. A cell design with lithium metal at the negative and a carbon substrate at the positive interface produced Coulombic efficiencies > 90% over 60 cycles. Finally, the beneficial effects of moderately elevated temperature were established where a 10 °C temperature increase led to ∼5× lower resistance.

A primary barrier preventing repetitive fast charging of Li-ion batteries is lithium metal plating at the graphite anode. One approach toward mitigating Li metal deposition is the deliberate modification of the graphite anode surface with materials demonstrating high overpotentials unfavorable for Li metal nucleation, such as Ni or Cu nanoscale films. This research explores Ni and Cu surface coatings at different areal loadings (3 or 11 μg cm−2) on the electrochemistry of graphite/LiNi0.6Mn0.2Co0.2O2 (NMC622) type Li-ion batteries. Extended galvanostatic cycling of control and metal-coated electrodes in graphite/NMC622 pouch cells are conducted under high rate conditions. Based on the overpotential of Li deposition on metal foil, both Ni and Cu treatments were anticipated to result in reduced lithium deposition. The higher metal film loadings of 11 μg cm−2 Ni- or Cu-coated electrodes exhibit the highest capacity retention after 500 cycles, with mean improvements of 8% and 9%, respectively, over uncoated graphite electrodes. Li plating quantified by X-ray diffraction indicates that the metal films effectively reduce the quantity of plated Li compared to untreated electrodes, with 11 μg cm−2 Cu providing the greatest benefit.

Future advances in energy storage systems rely on identification of appropriate target materials and deliberate synthesis of the target materials with control of their physiochemical properties in order to disentangle the contributions of distinct properties to the functional electrochemistry. This goal demands systematic inquiry using model materials that provide the opportunity for significant synthetic versatility and control. Ideally, a material family that enables direct manipulation of characteristics including composition, defects, and crystallite size while remaining within the defined structural framework would be necessary. Accomplishing this through direct synthetic methods is desirable to minimize the complicating effects of secondary processing. The structural motif most frequently used for insertion type electrodes is based on layered type structures where ion diffusion in two dimensions can be envisioned. However, lattice expansion and contraction associated with the ion movement and electron transfer as a result of repeated charge and discharge cycling can result in structural degradation and amorphization with accompanying loss of capacity. In contrast, tunnel type structures embody a more rigid framework where the inherent structural design can accommodate the presence of cations and often multiple cations. Of specific interest are manganese oxides as they can exhibit a tunneled structure, termed α-MnO

In this study, amorphous MoSx electrodes were fabricated by a facile one step electrodeposition method as sulfur equivalent cathode structures for lithium based batteries. By modifying the deposition conditions, the physical, chemical, and resulting electrochemical properties of MoSx were manipulated to achieve either higher energy delivery or higher power delivery. MoSx deposited at anodic potential (MoSx-AD) showed a higher initial capacity of 900 mAh g−1 attributed to its higher sulfur content. In contrast, MoSx deposited at cathodic potential (MoSx-CD) exhibited a lower initial capacity of 500 mAh g−1 with improved cycling stability up to 100 cycles and significantly improved rate capability attributed to its higher conductivity and improved Li+ transport properties.

Lithium solid-state composite electrolytes (LiSCEs) provide the opportunity for long life spans, low self-discharge, high reliability, high energy density, and safety. Additionally, this class of electrolytes can be used in electrolytically formed solid-state batteries (EFBs), which may promote reductions in cell manufacturing costs due to their simplicity of design and permit the formation of batteries with diverse architectures. Herein, we provide a discussion of LiSCEs, highlight some of the recent progress in EFB development, and present a forward outlook.

Electric energy storage systems such as batteries can significantly impact society in a variety of ways, including facilitating the widespread deployment of portable electronic devices, enabling the use of renewable energy generation for local off grid situations and providing the basis of highly efficient power grids integrated with energy production, large stationary batteries, and the excess capacity from electric vehicles. A critical challenge for electric energy storage is understanding the basic science associated with the gap between the usable output of energy storage systems and their theoretical energy contents. The goal of overcoming this inefficiency is to achieve more useful work (w) and minimize the generation of waste heat (q). Minimization of inefficiency can be approached at the macro level, where bulk parameters are identified and manipulated, with optimization as an ultimate goal. However, such a strategy may not provide insight toward the complexities of electric energy storage, especially the inherent heterogeneity of ion and electron flux contributing to the local resistances at numerous interfaces found at several scale lengths within a battery. Thus, the ability to predict and ultimately tune these complex systems to specific applications, both current and future, demands not just parametrization at the bulk scale but rather specific experimentation and understanding over multiple length scales within the same battery system, from the molecular scale to the mesoscale. Herein, we provide a case study examining the insights and implications from multiscale investigations of a prospective battery material, Fe3O4., The ability to predict and ultimately tune complex systems such as batteries demands understanding over multiple length scales including the structure (molecular), crystal (nanoscale), and agglomerate (mesoscale).