Lithiation Gradients and Tortuosity Factors in Thick NMC111-Argyrodite Solid-State Cathodes.

Achieving high energy density in all-solid-state lithium batteries will require the design of thick cathodes, and these will need to operate reversibly under normal use conditions. We use high-energy depth-profiling X-ray diffraction to measure the localized lithium content of Li1-xNi1/3Mn1/3Co1/3O2 (NMC111) through the thickness of 110 µm thick composite cathodes. The composite cathodes consisted of NMC111 of varying mass loadings mixed with argyrodite solid electrolyte Li6PS5Cl (LPSC). During cycling at C/10, substantial lithiation gradients developed, and varying the NMC111 loading altered the nature of these gradients. Microstructural analysis and cathode modeling showed this was due to high tortuosities in the cathodes. This was particularly true in the solid electrolyte phase, which experienced a marked increase in tortuosity factor during the initial charge. Our results demonstrate that current distributions are observed in sulfide-based composites and that these will be an important consideration for practical design of all-solid-state batteries.

Reversible Electrochemical Anionic Redox in Rechargeable Multivalent-Ion Batteries.

Rechargeable multivalent-ion batteries are of significant interest due to the high specific capacities and earth abundance of their metal anodes, though few cathode materials permit multivalent ions to electrochemically intercalate within them. The crystalline chevrel phases are among the few cathode materials known to reversibly intercalate multivalent cations. However, to date, no multivalent-ion intercalation electrodes can match their reversibility and stability, in part due to the lack of design rules that guide how ion intercalation and electron charge transfer are coupled up from the atomic scale. Here, we elucidate the electronic charge storage mechanism that occurs in chevrel phase (Mo6Se8, Mo6S8) electrodes upon the electrochemical intercalation of multivalent cations (Al3+, Zn2+), using solid-state nuclear magnetic resonance spectroscopy, synchrotron X-ray absorption near edge structure measurements, operando synchrotron diffraction, and density functional theory calculations. Upon cation intercalation, electrons are transferred selectively to the anionic chalcogen framework, while the transition metal octahedra are redox inactive. This reversible electrochemical anionic redox, which occurs without breaking or forming chemical bonds, is a fundamentally different charge storage mechanism than that occurring in most transition metal-containing intercalation electrodes using anionic redox to enhance energy density. The results suggest material design principles aimed at realizing new intercalation electrodes that enable the facile electrochemical intercalation of multivalent cations.

(De)lithiation of spinel ferrites Fe3O4, MgFe2O4, and ZnFe2O4: a combined spectroscopic, diffraction and theory study.

Iron based materials hold promise as next generation battery electrode materials for Li ion batteries due to their earth abundance, low cost, and low environmental impact. The iron oxide, magnetite Fe3O4, adopts the spinel (AB2O4) structure. Other 2+ cation transition metal centers can also occupy both tetrahedral and/or octahedral sites in the spinel structure including MgFe2O4, a partially inverse spinel, and ZnFe2O4, a normal spinel. Though structurally similar to Fe3O4 in the pristine state, previous studies suggest significant differences in structural evolution depending on the 2+ cation in the structure. This investigation involves X-ray absorption spectroscopy and X-ray diffraction affirmed by density functional theory (DFT) to elucidate the role of the 2+ cation on the structural evolution and phase transformations during (de)lithiation of the spinel ferrites Fe3O4, MgFe2O4, and ZnFe2O4. The cation in the inverse, normal and partially inverse spinel structures located in the tetrahedral (8a) site migrates to the previously unoccupied octahedral 16c site by 2 electron equivalents of lithiation, resulting in a disordered [A]16c[B2]16dO4 structure. DFT calculations support the experimental results, predicting full displacement of the 8a cation to the 16c site at 2 electron equivalents. Substitution of the 2+ cation results in segregation of oxidized phases in the charged state. This report provides significant structural insight into the (de)lithiation mechanisms for an intriguing class of iron oxide materials.

Energy dispersive X-ray diffraction (EDXRD) for operando materials characterization within batteries.

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.

Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4.

Magnetite, Fe3O4, holds significant interest as a Li-ion anode material because of its high theoretical capacity (926 mAh/g) associated with multiple electron transfers per cation center. Notably, both crystallite size and agglomeration influence ion transport. This report probes the effects of crystallite size (12 and 29 nm) and agglomeration on the reactions involved with the formation of the surface electrolyte interphase on Fe3O4. Isothermal microcalorimetry (IMC) was used to determine the parasitic heat evolved during lithiation by considering the total heat measured, cell polarization, and entropic contributions. Interestingly, the 29 nm Fe3O4-based electrodes produced more parasitic heat than the 12 nm samples (1346 vs 1155 J/g). This observation was explored using scanning electron microscopy (SEM) and X-ray fluorescence (XRF) mapping in conjunction with spatially resolved X-ray absorption spectroscopy (XAS). SEM imaging of the electrodes revealed more agglomerates for the 12 nm material, affirmed by XRF maps. Further, XAS results suggest that Li+ transport is more restricted for the smaller crystallite size (12 nm) material, attributed to its greater degree of agglomeration. These results rationalize the IMC data, where agglomerates of the 12 nm material limit solid electrolyte interphase formation and parasitic heat generation during lithiation of Fe3O4.

Reversible Electrochemical Lithium-Ion Insertion into the Rhenium Cluster Chalcogenide-Halide Re6Se8Cl2.

The cluster-based material Re6Se8Cl2 is a two-dimensional ternary material with cluster-cluster bonding across the a and b axes capable of multiple electron transfer accompanied by ion insertion across the c axis. The Li/Re6Se8Cl2 system showed reversible electron transfer from 1 to 3 electron equivalents (ee) at high current densities (88 mA/g). Upon cycling to 4 ee, there was evidence of capacity degradation over 50 cycles associated with the formation of an organic solid-electrolyte interface (between 1.45 and 1 V vs Li/Li+). This investigation highlights the ability of cluster-based materials with two-dimensional cluster bonding to be used in applications such as energy storage, showing structural stability and high rate capability.

Two-Dimensional Holey Nanoarchitectures Created by Confined Self-Assembly of Nanoparticles via Block Copolymers: From Synthesis to Energy Storage Property.

Advances in liquid-phase exfoliation and surfactant-directed anisotropic growth of two-dimensional (2D) nanosheets have enabled their rapid development. However, it remains challenging to develop assembly strategies that lead to the construction of 2D nanomaterials with well-defined geometry and functional nanoarchitectures that are tailored to specific applications. Here we report a facile self-assembly method leading to the controlled synthesis of 2D transition metal oxide (TMO) nanosheets containing a high density of holes. We utilize graphene oxide sheets as a sacrificial template and Pluronic copolymers as surfactants. By using ZnFe2O4 (ZFO) nanoparticles as a model material, we demonstrate that by tuning the molecular weight of the Pluronic copolymers we can incorporate the ZFO particles and tune the size of the holes in the sheets. The resulting 2D ZFO nanosheets offer synergistic characteristics including increased electrochemically active surface areas, shortened ion diffusion paths, and strong inherent mechanical properties, leading to enhanced lithium-ion storage properties. Postcycling characterization confirms that the samples maintain structural integrity after electrochemical cycling. Our findings demonstrate that this template-assisted self-assembly method is a useful bottom-up route for controlled synthesis of 2D nanoarchitectures, and these holey 2D nanoarchitectures are promising for improving the electrochemical performance of next-generation lithium-ion batteries.

Deliberately Designed Atomic-Level Silver-Containing Interface Results in Improved Rate Capability and Utilization of Silver Hollandite for Lithium-Ion Storage.

α-MnO2-structured materials are generally classified as semiconductors; thus, we present a strategy to increase electrochemical utilization through the design of a conductive material interface. Surface treatment of silver hollandite (AgxMn8O16) with Ag+ (Ag2O) provides significant benefits to the resultant electrochemistry, including a decreased charge-transfer resistance and a 2-fold increase in deliverable energy density at a high rate. The improved function of this designed interface relative to conventional electrode fabrication strategies is highlighted.

Visualization of structural evolution and phase distribution of a lithium vanadium oxide (Li1.1V3O8) electrode via an operando and in situ energy dispersive X-ray diffraction technique.

Li1+nV3O8 (n = 0-0.2) has been extensively investigated as a cathode material for Li ion batteries because of its superior electrochemical properties including high specific energy and good rate capability. In this paper, a synchrotron based energy dispersive X-ray diffraction (EDXRD) technique was employed to profile the phase transitions and the spatial phase distribution of a Li1.1V3O8 electrode during electrochemical (de)lithiation in situ and operando. As annealing temperature during the preparation of the Li1.1V3O8 material has a strong influence on the morphology and crystallinity, and consequently influences the electrochemical outcomes of the material, Li1.1V3O8 materials prepared at two different temperatures, 500 and 300 °C (LVO500 and LVO300), were employed in this study. The EDXRD spectra of LVO500 and LVO300 cells pre-discharged at C/18, C/40 and C/150 were recorded in situ, and phase localization and relative intensity of the peaks were compared. For cells discharged at the C/18 rate, although α and ß phases were distributed uniformly within the LVO500 electrode, they were localized on two sides of the LVO300 electrode. Discharging rates of C/40 and C/150 led to homogeneous ß phase formation in both LVO500 and LVO300 electrodes. Furthermore, the phase distribution as a function of position and (de)lithiation extent was mapped operando as the LVO500 cell was (de)lithiated. The operando data indicate that (1) the lithiation reaction initiated from the side of the electrode facing the Li anode and proceeded towards the side facing the steel can, (2) during discharge the phase transformation from a Li-poor to a Li-rich α phase and the formation of a ß phase can proceed simultaneously in the electrode after the first formation of a ß phase, and (3) the structural evolution occurring during charging is not the reverse of that during discharge and takes place homogenously throughout the electrode.

A Tunable 3D Nanostructured Conductive Gel Framework Electrode for High-Performance Lithium Ion Batteries.

This study develops a tunable 3D nanostructured conductive gel framework as both binder and conductive framework for lithium ion batteries. A 3D nanostructured gel framework with continuous electron pathways can provide hierarchical pores for ion transport and form uniform coatings on each active particle against aggregation. The hybrid gel electrodes based on a polypyrrole gel framework and Fe3 O4 nanoparticles as a model system in this study demonstrate the best rate performance, the highest achieved mass ratio of active materials, and the highest achieved specific capacities when considering total electrode mass, compared to current literature. This 3D nanostructured gel-based framework represents a powerful platform for various electrochemically active materials to enable the next-generation high-energy batteries.

Nanostructured Conductive Polymer Gels as a General Framework Material To Improve Electrochemical Performance of Cathode Materials in Li-Ion Batteries.

Controlling architecture of electrode composites is of particular importance to optimize both electronic and ionic conduction within the entire electrode and improve the dispersion of active particles, thus achieving the best energy delivery from a battery. Electrodes based on conventional binder systems that consist of carbon additives and nonconductive binder polymers suffer from aggregation of particles and poor physical connections, leading to decreased effective electronic and ionic conductivities. Here we developed a three-dimensional (3D) nanostructured hybrid inorganic-gel framework electrode by in situ polymerization of conductive polymer gel onto commercial lithium iron phosphate particles. This framework electrode exhibits greatly improved rate and cyclic performance because the highly conductive and hierarchically porous network of the hybrid gel framework promotes both electronic and ionic transport. In addition, both inorganic and organic components are uniformly distributed within the electrode because the polymer coating prevents active particles from aggregation, enabling full access to each particle. The robust framework further provides mechanical strength to support active electrode materials and improves the long-term electrochemical stability. The multifunctional conductive gel framework can be generalized for other high-capacity inorganic electrode materials to enable high-performance lithium ion batteries.

Octa-µ3-selenido-penta-kis-(tri-ethyl-phos-phane-κP)(tri-methyl-aceto-nitrile-κN)-octa-hedro-hexa-rhenium(III) bis-(hexa-fluorido-anti-monate) tri-methyl-aceto-nitrile monosolvate.

The crystal structure of the title compound, [Re6Se8{NCC(CH3)3}(Et3P)5](SbF6)2·NCC(CH3)3, contains a face-capped octa-hedral [Re6(µ3-Se)8](2+) cluster core. The pseudo-centrosymmetric [Re6Se8](2+) cluster core is bonded through the Re atoms to five tri-ethyl-phosphane ligands and one tri-methyl-aceto-nitrile ligand. No significant interactions are observed between the cationic cluster, the SbF6 (-) anions and the trimethylacetonitrile solvent molecule.