Toward Quantitative Electrodeposition via In Situ Liquid Phase Transmission Electron Microscopy: Studying Electroplated Zinc Using Basic Image Processing and 4D STEM.

High energy density electrochemical systems such as metal batteries suffer from uncontrollable dendrite growth on cycling, which can severely compromise battery safety and longevity. This originates from the thermodynamic preference of metal nucleation on electrode surfaces, where obtaining the crucial information on metal deposits in terms of crystal orientation, plated volume, and growth rate is very challenging. In situ liquid phase transmission electron microscopy (LPTEM) is a promising technique to visualize and understand electrodeposition processes, however a detailed quantification of which presents significant difficulties. Here by performing Zn electroplating and analyzing the data via basic image processing, this work not only sheds new light on the dendrite growth mechanism but also demonstrates a workflow showcasing how dendritic deposition can be visualized with volumetric and growth rate information. These results along with additionally corroborated 4D STEM analysis take steps to access information on the crystallographic orientation of the grown Zn nucleates and toward live quantification of in situ electrodeposition processes.

Lightweight Carbon-Metal-Based Fabric Anode for Lithium-Ion Batteries.

Lithium-ion battery electrodes are typically manufactured via slurry casting, which involves mixing active material particles, conductive carbon, and a polymeric binder in a solvent, followed by casting and drying the coating on current collectors (Al or Cu). These electrodes are functional but still limited in terms of pore network percolation, electronic connectivity, and mechanical stability, leading to poor electron/ion conductivities and mechanical integrity upon cycling, which result in battery degradation. To address this, we fabricate trichome-like carbon-iron fabrics via a combination of electrospinning and pyrolysis. Compared with slurry cast Fe2O3 and graphite-based electrodes, the carbon-iron fabric (CMF) electrode provides enhanced high-rate capacity (10C and above) and stability, for both half cell and full cell testing (the latter with a standard lithium nickel manganese oxide (LNMO) cathode). Further, the CMFs are free-standing and lightweight; therefore, future investigation may include scaling this as an anode material for pouch cells and 18,650 cylindrical batteries.

Effect of Low Environmental Pressure on Sintering Behavior of NASICON-Type Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolytes: An In Situ ESEM Study.

Solid-state sintering at high temperatures is commonly used to densify solid electrolytes. Yet, optimizing phase purity, structure, and grain sizes of solid electrolytes is challenging due to the lack of understanding of relevant processes during sintering. Here, we use an in situ environmental scanning electron microscopy (ESEM) to monitor the sintering behavior of NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) at low environmental pressures. Our results show that while no major morphological changes are observed at 10-2 Pa and only coarsening is induced at 10 Pa, environmental pressures of 300 and 750 Pa lead to the formation of typically sintered LATP electrolytes. Furthermore, the use of pressure as an additional parameter in sintering allows the grain size and shape of electrolyte particles to be controlled.

Screening of Coatings for an All-Solid-State Battery using In Situ Transmission Electron Microscopy.

With the ever-increasing use of Li-ion batteries, especially due to their adoption in electric vehicles, their safety is in prime focus. Thus, the all-solid-state batteries (ASSBs) that use solid electrolytes instead of liquid electrolytes, which reduce the risk of flammability, have been the center stage of battery research for the last few years. However, in the ASSB, the ion transportation through the solid-solid electrolyte-electrode interface poses a challenge due to contact and chemical/electrochemical stability issues. Applying a suitable coating around the electrode and/or electrolyte particles offers a convenient solution, leading to better performance. For this, researchers are screening potential electronic/ionic conductive and nonconductive coatings to find the best coatings with suitable thickness for long-term chemical, electrochemical, and mechanical stability. Operando transmission electron microscopy (TEM) couples high spatial resolution with high temporal resolution to allow visualization of dynamic processes, and thus is an ideal tool to evaluate electrode/electrolyte coatings via studying (de)lithiation at a single particle level in real-time. However, the accumulated electron dose during a typical high-resolution in situ work may affect the electrochemical pathways, evaluation of which can be time-consuming. The current protocol presents an alternative procedure in which the potential coatings are applied on Si nanoparticles and are subjected to (de)lithiation during operando TEM experiments. The high volume changes of Si nanoparticles during (de)lithiation allow monitoring of the coating behavior at a relatively low magnification. Thus, the whole process is very electron-dose efficient and offers quick screening of potential coatings.

Operando transmission electron microscopy of battery cycling: thickness dependent breaking of TiO2 coating on Si/SiO2 nanoparticles.

Conformal coating of silicon (Si) anode particles is a common strategy for improving their mechanical integrity, to mitigate battery capacity fading due to particle volume expansion, which can result in particle crumbling due to lithiation induced strain and excessive solid-electrolyte interface formation. Here, we use operando transmission electron microscopy in an open cell to show that TiO2 coatings on Si/SiO2 particles undergo thickness dependent rupture on battery cycling where thicker coatings crumble more readily than thinner (∼5 nm) coatings, which corroborates the difference in their capacities.

Thermal evolution of NASICON type solid-state electrolytes with lithium at high temperature via in situ scanning electron microscopy.

We present the thermal evolution of two NASICON-type ceramics namely LATP (Li1+xAlxTi2-x(PO4)3) and LAGP (Li1+xAlxGe2-x(PO4)3) by monitoring the electrode-electrolyte interfaces (i.e., Li/LATP and Li/LAGP) at temperatures up to 330 °C via in situ scanning electron microscopy, post-mortem energy-dispersive spectroscopy, and X-ray diffraction. Upon melting of Li and contacting electrolytes, LAGP decomposes completely to form Li based alloys, while LATP is partially decomposed without alloying.

Hybrid Redox Flow Cells with Enhanced Electrochemical Performance via Binderless and Electrophoretically Deposited Nitrogen-Doped Graphene on Carbon Paper Electrodes.

Hybrid redox flow cells (HRFC) are key enablers for the development of reliable large-scale energy storage systems; however, their high cost, limited cycle performance, and incompatibilities associated with the commonly used carbon-based electrodes undermine HRFC's commercial viability. While this is often linked to lack of suitable electrocatalytic materials capable of coping with HRFC electrode processes, the combinatory use of nanocarbon additives and carbon paper electrodes holds new promise. Here, by coupling electrophoretically deposited nitrogen-doped graphene (N-G) with carbon electrodes, their surprisingly beneficial effects on three types of HRFCs, namely, hydrogen/vanadium (RHVFC), hydrogen/manganese (RHMnFC), and polysulfide/air (S-Air), are revealed. RHVFCs offer efficiencies over 70% at a current density of 150 mA cm-2 and an energy density of 45 Wh L-1 at 50 mA cm-2, while RHMnFCs achieve a 30% increase in energy efficiency (at 100 mA cm-2). The S-Air cell records an exchange current density of 4.4 × 10-2 mA cm-2, a 3-fold improvement of kinetics compared to the bare carbon paper electrode. We also present cost of storage at system level compared to the standard all-vanadium redox flow batteries. These figures-of-merit can incentivize the design, optimization, and adoption of high-performance HRFCs for successful grid-scale or renewable energy storage market penetration.

Scalable Route to Electroactive and Light Active Perylene Diimide Dye Polymer Binder for Lithium-Ion Batteries.

Developing multifunctional polymeric binders is key to the design of energy storage technologies with value-added features. We report that a multigram-scale synthesis of perylene diimide polymer (PPDI), from a single batch via polymer analogous reaction route, yields high molecular weight polymers with suitable thermal stability and minimized solubility in electrolytes, potentially leading to improved binding affinity toward electrode particles. Further, it develops strategies for designing copolymers with virtually any desired composition via a subsequent grafting, leading to purpose-built binders. PPDI dye as both binder and electroactive additive in lithium half-cells using lithium iron phosphate exhibits good electrochemical performance.

Spatiotemporal Quantification of Lithium both in Electrode and in Electrolyte with Atomic Precision via Operando Neutron Absorption.

The commercial uptake of lithium-sulfur (Li-S) batteries is undermined by their rapid performance decay and short cycle life. These problems originate from the dissolution of lithium polysulfide in liquid electrolytes, causing charge and active material to shuttle between electrodes. The dynamics of intractable polysulfide migration at different length scales often tend to escape the probing ability of many analytical techniques. Spatial and temporal visualization of Li in Li-S electrodes and direct mechanistic understanding of how polysulfides are regulated across Li-S batteries starting from current collector and active layer coating to electrode-electrolyte interface are still lacking. To address this we employ neutron depth profiling across Li-S electrodes using the naturally occurring isotope, 6Li, which yields direct spatial information on Li-S electrochemistry. Using three types of Li-S electrodes, namely, carbon-sulfur, carbon-sulfur with 10% lithium titanium oxide (LTO), and carbon-sulfur with LTO membrane, we provide direct evidence for the migration, adsorption, and confinement of polysulfides in Li-S cells at work. Our findings further provide insights into the dynamics of polysulfide dissolution and re-utilization in relation to Li-S battery capacity and longevity to aid rational electrode designs toward high-energy, safe, and low-cost batteries.

Photo-Rechargeable Organo-Halide Perovskite Batteries.

Emerging autonomous electronic devices require increasingly compact energy generation and storage solutions. Merging these two functionalities in a single device would significantly increase their volumetric performance, however this is challenging due to material and manufacturing incompatibilities between energy harvesting and storage materials. Here we demonstrate that organic-inorganic hybrid perovskites can both generate and store energy in a rechargeable device termed a photobattery. This photobattery relies on highly photoactive two-dimensional lead halide perovskites to simultaneously achieve photocharging and Li-ion storage. Integrating these functionalities provides simple autonomous power solutions while retaining capacities of up to 100 mAh/g and efficiencies similar to electrodes using a mixture of batteries and solar materials.

Evolution of Reduced Graphene Oxide-SnS2 Hybrid Nanoparticle Electrodes in Li-Ion Batteries.

Hybrid nanomaterials where active battery nanoparticles are synthesized directly onto conductive additives such as graphene hold the promise of improving the cyclability and energy density of conversion and alloying type Li-ion battery electrodes. Here we investigate the evolution of hybrid reduced graphene oxide-tin sulfide (rGO-SnS2) electrodes during battery cycling. These hybrid nanoparticles are synthesized by a one-step solvothermal microwave reaction which allows for simultaneous synthesis of the SnS2 nanocrystals and reduction of GO. Despite the hybrid architecture of these electrodes, electrochemical impedance spectroscopy shows that the impedance doubles in about 25 cycles and subsequently gradually increases, which may be caused by an irreversible surface passivation of rGO by sulfur enriched conversion products. This surface passivation is further confirmed by post-mortem Raman spectroscopy of the electrodes, which no longer detects rGO peaks after 100 cycles. Moreover, galvanostatic intermittent titration analysis during the 1st and 100th cycles shows a drop in Li-ion diffusion coefficient of over an order of magnitude. Despite reports of excellent cycling performance of hybrid nanomaterials, our work indicates that in certain electrode systems, it is still critical to further address passivation and charge transport issues between the active phase and the conductive additive in order to retain high energy density and cycling performance.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Structural Evolution of Electrochemically Lithiated MoS2 Nanosheets and the Role of Carbon Additive in Li-Ion Batteries.

Understanding the structure and phase changes associated with conversion-type materials is key to optimizing their electrochemical performance in Li-ion batteries. For example, molybdenum disulfide (MoS2) offers a capacity up to 3-fold higher (∼1 Ah/g) than the currently used graphite anodes, but they suffer from limited Coulombic efficiency and capacity fading. The lack of insights into the structural dynamics induced by electrochemical conversion of MoS2 still hampers its implementation in high energy-density batteries. Here, by combining ab initio density-functional theory (DFT) simulation with electrochemical analysis, we found new sulfur-enriched intermediates that progressively insulate MoS2 electrodes and cause instability from the first discharge cycle. Because of this, the choice of conductive additives is critical for the battery performance. We investigate the mechanistic role of carbon additive by comparing equal loading of standard Super P carbon powder and carbon nanotubes (CNTs). The latter offer a nearly 2-fold increase in capacity and a 45% reduction in resistance along with Coulombic efficiency of over 90%. These insights into the phase changes during MoS2 conversion reactions and stabilization methods provide new solutions for implementing cost-effective metal sulfide electrodes, including Li-S systems in high energy-density batteries.

Flexible Batteries: Hierarchical Assemblies of Carbon Nanotubes for Ultraflexible Li-Ion Batteries (Adv. Mater. 31/2016).

An advanced battery architecture composed of 3D carbon nanotube (CNT) current collectors is used to mitigate stresses in flexible batteries. On Page 6705, C. George, M. De Volder, and co-workers describe the fabrication process and characteristics of this new generation of ultraflexible batteries, which show high rate and cyclablility. These batteries may find applications in the powering of flexible displays and logics.

Hierarchical Assemblies of Carbon Nanotubes for Ultraflexible Li-Ion Batteries.

The flexible batteries that are needed to power flexible circuits and displays remain challenging, despite considerable progress in the fabrication of such devices. Here, it is shown that flexible batteries can be fabricated using arrays of carbon nanotube microstructures, which decouple stress from the energy-storage material. It is found that this battery architecture imparts exceptional flexibility (radius ≈ 300 µm), high rate (20 A g(-1) ), and excellent cycling stability.

Morphology-Dependent Electrochemical Properties of CuS Hierarchical Superstructures.

Hierarchical superstructures formed by self-assembled nanoparticles exhibit interesting electrochemical properties that can potentially be exploited in Li-ion batteries (LIBs) as possible electrode materials. In this work, we tested two different morphologies of CuS superstructures for electrodes, namely, tubular dandelion-like and ball-like assemblies, both of which are composed of similar small covellite nanoparticles. These two CuS morphologies are characterized by their markedly different electrochemical performances, suggesting that their complex structures/morphologies influence the electrochemical properties. At 1.12 A g(-1), the cells made with CuS tubular structures delivered about 420 mAh g(-1), and at 0.56 A g(-1), the capacity was as high as about 500 mAh g(-1) with good capacity retention. Their ease of preparation and processing, together with good electrochemical performance, make CuS tubular dandelion-like clusters attractive for developing low-cost LIBs based on conversion reactions.

From Binary Cu2S to ternary Cu-In-S and quaternary Cu-In-Zn-S nanocrystals with tunable composition via partial cation exchange.

We present an approach for the synthesis of ternary copper indium sulfide (CIS) and quaternary copper indium zinc sulfide (CIZS) nanocrystals (NCs) by means of partial cation exchange with In(3+) and Zn(2+). The approach consists of a sequential three-step synthesis: first, binary Cu2S NCs were synthesized, followed by the homogeneous incorporation of In(3+) by an in situ partial cation-exchange reaction, leading to CIS NCs. In the last step, a second partial exchange was performed where Zn(2+) partially replaced the Cu(+) and In(3+) cations at the surface, creating a ZnS-rich shell with the preservation of the size and shape. By careful tuning reaction parameters (growth and exchange times as well as the initial Cu(+):In(3+):Zn(2+) ratios), control over both the size and composition was achieved. This led to a broad tuning of photoluminescence of the final CIZS NCs, ranging from 880 to 1030 nm without altering the NCs size. Cytotoxicity tests confirmed the biocompatibility of the synthesized CIZS NCs, which opens up opportunities for their application as near-infrared fluorescent markers in the biomedical field.

Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼ 155 mAh/g, ∼ 135 mAh/g, and ∼ 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼ 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼ 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries.

Alloyed copper chalcogenide nanoplatelets via partial cation exchange reactions.

We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide-sulfide (CZSeS), copper tin selenide-sulfide (CTSeS), and copper zinc tin selenide-sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide-sulfide (Cu2-xSeyS1-y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2-xSeyS1-y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV-vis-NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps.

Redox centers evolution in phospho-olivine type (LiFe0.5Mn0.5 PO4) nanoplatelets with uniform cation distribution.

In phospho-olivine type structures with mixed cations (LiM1M2PO4), the octahedral M1 and M2 sites that dictate the degree of intersites order/disorder play a key role in determining their electrochemical redox potentials. In the case of LiFexMn1-xPO4, for example, in micrometer-sized particles synthesized via hydrothermal route, two separate redox centers corresponding to Fe(2+)/Fe(3+) (3.5 V vs Li/Li(+)) and Mn(2+)/Mn(3+) (4.1 V vs Li/Li(+)), due to the collective Mn-O-Fe interactions in the olivine lattice, are commonly observed in the electrochemical measurements. These two redox processes are directly reflected as two distinct peak potentials in cyclic voltammetry (CV) and equivalently as two voltage plateaus in their standard charge/discharge characteristics (in Li ion batteries). On the contrary, we observed a single broad peak in CV from LiFe0.5Mn0.5PO4 platelet-shaped (∼10 nm thick) nanocrystals that we are reporting in this work. Structural and compositional analysis showed that in these nanoplatelets the cations (Fe, Mn) are rather homogeneously distributed in the lattice, which is apparently the reason for a synergetic effect on the redox potentials, in contrast to LiFe0.5Mn0.5PO4 samples obtained via hydrothermal routes. After a typical carbon-coating process in a reducing atmosphere (Ar/H2), these LiFe0.5Mn0.5PO4 nanoplatelets undergo a rearrangement of their cations into Mn-rich and Fe-rich domains. Only after such cation rearrangement (via segregation) in the nanocrystals, the redox processes evolved at two distinct potentials, corresponding to the standard Fe(2+)/Fe(3+) and Mn(2+)/Mn(3+) redox centers. Our experimental findings provide new insight into mixed-cation olivine structures in which the degree of cations mixing in the olivine lattice directly influences the redox potentials, which in turn determine their charge/discharge characteristics.