David C. Bock

In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism

Watching the silver lining inside Some types of batteries contain both a transition metal reducible metal, such as the cathode material Ag2VP2O8. During operation, both Ag and V ions are reduced, and the Ag atoms can form wires to enhance the internal conductivity. Kirshenbaum et al. probe the discharge of a battery at different rates and track the formation of Ag atoms using in situ energy-dispersive x-ray diffraction (see the Perspective by Dudney and Li). They show how the discharge rate affects whether the Ag or V is preferentially reduced and also the distribution of the Ag atoms, and then correlate this to the loss of battery capacity at higher discharge rates. Science, this issue p. 149; see also p. 131 The change in battery capacity with discharge rate is related to internal structural changes using in situ imaging. [Also see Perspective by Dudney and Li] The functional capacity of a battery is observed to decrease, often quite dramatically, as discharge rate demands increase. These capacity losses have been attributed to limited ion access and low electrical conductivity, resulting in incomplete electrode use. A strategy to improve electronic conductivity is the design of bimetallic materials that generate a silver matrix in situ during cathode reduction. Ex situ x-ray absorption spectroscopy coupled with in situ energy-dispersive x-ray diffraction measurements on intact lithium/silver vanadium diphosphate (Li/Ag2VP2O8) electrochemical cells demonstrate that the metal center preferentially reduced and its location in the bimetallic cathode are rate-dependent, affecting cell impedance. This work illustrates that spatial imaging as a function of discharge rate can provide needed insights toward improving realizable capacity of bimetallic cathode systems.

2D Cross Sectional Analysis and Associated Electrochemistry of Composite Electrodes Containing Dispersed Agglomerates of Nanocrystalline Magnetite, Fe3O4

When electroactive nanomaterials are fully incorporated into an electrode structure, characterization of the crystallite sizes, agglomerate sizes, and dispersion of the electroactive materials can lend insight into the complex electrochemistry associated with composite electrodes. In this study, composite magnetite electrodes were sectioned using ultramicrotome techniques, which facilitated the direct observation of crystallites and agglomerates of magnetite (Fe3O4) as well as their dispersal patterns in large representative sections of electrode, via 2D cross sectional analysis by Transmission Electron Microscopy (TEM). Further, the electrochemistry of these electrodes were recorded, and Transmission X-ray Microscopy (TXM) was used to determine the distribution of oxidation states of the reduced magnetite. Unexpectedly, while two crystallite sizes of magnetite were employed in the production of the composite electrodes, the magnetite agglomerate sizes and degrees of dispersion in the two composite electrodes were similar to each other. This observation illustrates the necessity for careful characterization of composite electrodes, in order to understand the effects of crystallite size, agglomerate size, and level of dispersion on electrochemistry.

Dispersion of Nanocrystalline Fe3O4 within Composite Electrodes: Insights on Battery-Related Electrochemistry

Aggregation of nanosized materials in composite lithium-ion-battery electrodes can be a significant factor influencing electrochemical behavior. In this study, aggregation was controlled in magnetite, Fe3O4, composite electrodes via oleic acid capping and subsequent dispersion in a carbon black matrix. A heat treatment process was effective in the removal of the oleic acid capping agent while preserving a high degree of Fe3O4 dispersion. Electrochemical testing showed that Fe3O4 dispersion is initially beneficial in delivering a higher functional capacity, in agreement with continuum model simulations. However, increased capacity fade upon extended cycling was observed for the dispersed Fe3O4 composites relative to the aggregated Fe3O4 composites. X-ray absorption spectroscopy measurements of electrodes post cycling indicated that the dispersed Fe3O4 electrodes are more oxidized in the discharged state, consistent with reduced reversibility compared with the aggregated sample. Higher charge-transfer resistance for the dispersed sample after cycling suggests increased surface-film formation on the dispersed, high-surface-area nanocrystalline Fe3O4 compared to the aggregated materials. This study provides insight into the specific effects of aggregation on electrochemistry through a multiscale view of mechanisms for magnetite composite electrodes.

Effective recycling of manganese oxide cathodes for lithium based batteries

While rechargeable lithium ion batteries (LIBs) occupy a prominent consumer presence due to their high cell potential and gravimetric energy density, there are limited opportunities for electrode recycling. Currently used or proposed cathode recycling processes are multistep procedures which involve sequences of mechanical, thermal, and chemical leaching, where only the base material is recovered and significant processing is required to generate a recycled electrode structure. Another significant issue facing lithium based batteries is capacity fade due to structural degradation of the electroactive material upon extending cycling. Herein, inspired by heterogeneous catalyst thermal regeneration strategies, we present a new facile cathode recycling process, where previously used cathodes are removed from a cell, heat treated, and then inserted into a new cell restoring the delivered capacity and cycle life. An environmentally sustainable manganese based material is employed, where binder-free self-supporting (BFSS) electrodes are prepared using a fibrous, high aspect ratio manganese oxide active material. After 200 discharge–charge cycles, the recycled BFSS electrodes display restored crystallinity and oxidation state of the manganese centers with the resulting electrochemistry (capacity and coulombic efficiency) reminiscent of freshly prepared BFSS cathodes. Notably, the BFSS electrode structure is robust with no degradation during the cell disassembly, electrode recovery, washing, and heat treatment steps; thus no post-processing is required for the recycled electrode. This work shows for the first time that a thermal regeneration method previously employed in catalyst systems can fully restore battery electrochemical performance, demonstrating a novel electrode recycling process which could open up new possibilities for energy storage devices with extended electrode lifecycles.

Investigating the Complex Chemistry of Functional Energy Storage Systems: The Need for an Integrative, Multiscale (Molecular to Mesoscale) Perspective

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.

Electrochemical reduction of Ag2VP2O8 composite electrodes visualized via in situ energy dispersive X-ray diffraction (EDXRD): unexpected conductive additive effects

In this study, we characterize the deposition of silver metal nanoparticles formed during discharge of Li/Ag2VP2O8 cells with composite cathodes containing conductive carbon additive. Using in situ energy dispersive X-ray diffraction (EDXRD) of an intact battery, the location and distribution of silver metal nanoparticles generated upon reduction-displacement deposition within an Ag2VP2O8 cathode containing a pre-existing percolation network can be observed for the first time. This study yielded unexpected results where higher rate initial discharge generated a more effective conductive matrix. This stands in contrast to cells with cathodes with no conductive additive where a low rate initial discharge proved more effective. These results provide evidence that using conductive additives in conjunction with an in situ reduction-displacement deposition of silver metal provides a path toward the ultimate goal of complete electrical contact and full utilization of all electroactive particles.

Mapping the anode surface-electrolyte interphase: investigating a life limiting process of lithium primary batteries.

Cathode solubility in batteries can lead to decreased and unpredictable long-term battery behavior due to transition metal deposition on the negative electrode such that it no longer supports high current. Analysis of negative electrodes from cells containing vanadium oxide or phosphorus oxide based cathode systems retrieved after long-term testing was conducted. This report demonstrates the use of synchrotron based X-ray microfluorescence (XRμF) to map negative battery electrodes in conjunction with microbeam X-ray absorption spectroscopy (μXAS) to determine the oxidation states of the metal centers resident in the solid electrolyte interphase (SEI) and at the electrode surface. Based on the empirical findings, a conceptual model for the location of metal ions in the SEI and their role in impacting lithium ion mobility at the electrode surfaces is proposed.

Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

In this study, we utilize silver vanadium phosphorous oxide, Ag2VO2PO4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Three different electrode compositions were investigated: Ag2VO2PO4 only, Ag2VO2PO4 with binder, and Ag2VO2PO4 with binder and carbon. Constant current discharge, pulse testing and impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag0 formed. Results indicate that the metal center reduced (V5+ or Ag+) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag0 nanoparticle formation), and spatial location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag0. This study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.

Synthesis and Characterization of CuFe2O4 Nano/Submicron Wire–Carbon Nanotube Composites as Binder-free Anodes for Li-Ion Batteries

A series of one-dimensional CuFe2O4 (CFO) nano/submicron wires possessing different diameters, crystal phases, and crystal sizes have been successfully generated using a facile template-assisted coprecipitation reaction at room temperature, followed by a short postannealing process. The diameter and crystal structure of the resulting CuFe2O4 (CFO) wires were judiciously tuned by varying the pore size of the template and the postannealing temperature, respectively. Carbon nanotubes (CNTs) were incorporated to generate CFO-CNT binder-free anodes, and multiple characterization techniques were employed with the goal of delineating the relationships between electrochemical behavior and the properties of both the CFO wires (crystal phase, wire diameter, crystal size) and the electrode architecture (binder-free vs conventionally prepared approaches). The study reveals several notable findings. First, the crystal phase (cubic or tetragonal) did not influence the electrochemical behavior in this CFO system. Second, regarding crystallite size and wire diameter, CFO wires with larger crystallite sizes exhibit improved cycling stability, whereas wires possessing smaller diameters exhibit higher capacities. Finally, the electrochemical behavior is strongly influenced by the electrode architecture, with CFO-CNT binder-free electrodes demonstrating significantly higher capacities and cycling stability compared to conventionally prepared coatings. The mechanism(s) associated with the high capacities under low current density but limited electrochemical reversibility of CFO electrodes under high current density were probed via X-ray absorption spectroscopy mapping with submicron spatial resolution for the first time. Results suggest that the capacity of the binder-free electrodes under high rate is limited by the irreversible formation of Cu0, as well as limited reduction of Fe3+ to Fe2+, not Fe0. The results (1) shed fundamental insight into the reversibility of CuFe2O4 materials cycled at high current density and (2) demonstrate that a synergistic effort to control both active material morphology and electrode architecture is an effective strategy for optimizing electrochemical behavior.

X-ray induced chemical reaction revealed by in-situ X-ray diffraction and scanning X-ray microscopy in 15 nm resolution(Conference Presentation)

The detection sensitivity of synchrotron-based X-ray techniques has been largely improved due to the ever increasing source brightness, which have significantly advanced ex-situ and in-situ research for energy materials, such as lithium-ion batteries. However, the strong beam-matter interaction arisen from the high beam flux can significantly modify the material structure. The parasitic beam-induced effect inevitably interferes with the intrinsic material property, which brings difficulties in interpreting experimental results, and therefore requires comprehensive evaluation. Here we present a quantitative in-situ study of the beam-effect on one electrode material Ag2VO2PO4 using four different X-ray probes with different radiation dose rate. The material system we reported exhibits interesting and reversible radiation-induced thermal and chemical reactions, which was further evaluated under electron microscopy to illustrate the underlying mechanism. The work we presented here will provide a guideline in using synchrotron X-rays to distinguish the materials’ intrinsic behavior from extrinsic structure changed induced by X-rays, especially in the case of in-situ and operando study where the materials are under external field of either temperature or electric field.