Physicochemical Heterogeneity in Silicon Anodes from Cycled Lithium-Ion Cells.

The severe capacity fade of lithium-ion cells with silicon-dominant anodes has hindered their widescale commercialization. In this work, we link cell capacity fade to the heterogeneous physicochemical evolution of silicon anodes during battery cycling. Through a multilength scale characterization approach, we demonstrate that silicon particles near the anode surface react differently from those near the copper current collector. In particular, near the anode surface we find an amorphized wispy silicon encased in a highly fluorinated matrix of electrolyte-reduction products. In contrast, closer to the current collector, the silicon retains more of its initial morphology and structure, suggesting the presence of isolated particles. The results show that the accessibility of active silicon to lithium ions varies across the anode matrix. Material and cell designs, which minimize electrode expansion resulting from the in-filling of pores with the solid electrolyte interphase (SEI), are needed to enhance anode homogeneity during the electrochemical cycling.

In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy.

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate multiple processes responsible for long-term performance decay. Given the complexity of physical processes occurring inside the cell, it is often challenging to achieve a full understanding of the root causes of this performance degradation. This difficulty arises in part from the fact that any electrochemical measurement of a battery will return the combined contributions of all components in the cell. Incorporation of a reference electrode can solve part of the problem, as it allows the electrochemical reactions of the cathode and the anode to be individually probed. A variation in the voltage range experienced by the cathode, for example, can indicate alterations in the pool of cyclable lithium ions in the full-cell. The structural evolution of the many interphases existing in the battery can also be monitored, by measuring the contributions of each electrode to the overall cell impedance. Such wealth of information amplifies the reach of diagnostic analysis in Li-ion batteries and provides valuable input to the optimization of individual cell components. In this work, we introduce the design of a test cell able to accommodate multiple reference electrodes, and present reference electrodes that are appropriate for each specific type of measurement, detailing the assembly process in order to maximize the accuracy of the experimental results.

Curious Case of Positive Current Collectors: Corrosion and Passivation at High Temperature.

In the evaluation of compatibility of different components of cell for high-energy and extreme-conditions applications, the highly focused are positive and negative electrodes and their interaction with electrolyte. However, for high-temperature application, the other components are also of significant influence and contribute toward the total health of battery. In present study, we have investigated the behavior of aluminum, the most common current collector for positive electrode materials for its electrochemical and temperature stability. For electrochemical stability, different electrolytes, organic and room temperature ionic liquids with varying Li salts (LiTFSI, LiFSI), are investigated. The combination of electrochemical and spectroscopic investigations reflects the varying mechanism of passivation at room and high temperature, as different compositions of decomposed complexes are found at the surface of metals.

Ionic Liquid-Organic Carbonate Electrolyte Blends To Stabilize Silicon Electrodes for Extending Lithium Ion Battery Operability to 100 °C.

Fabrication of lithium-ion batteries that operate from room temperature to elevated temperatures entails development and subsequent identification of electrolytes and electrodes. Room temperature ionic liquids (RTILs) can address the thermal stability issues, but their poor ionic conductivity at room temperature and compatibility with traditional graphite anodes limit their practical application. To address these challenges, we evaluated novel high energy density three-dimensional nano-silicon electrodes paired with 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide (Pip) ionic liquid/propylene carbonate (PC)/LiTFSI electrolytes. We observed that addition of PC had no detrimental effects on the thermal stability and flammability of the reported electrolytes, while largely improving the transport properties at lower temperatures. Detailed investigation of the electrochemical properties of silicon half-cells as a function of PC content, temperature, and current rates reveal that capacity increases with PC content and temperature and decreases with increased current rates. For example, addition of 20% PC led to a drastic improvement in capacity as observed for the Si electrodes at 25 °C, with stability over 100 charge/discharge cycles. At 100 °C, the capacity further increases by 3-4 times to 0.52 mA h cm(-2) (2230 mA h g(-1)) with minimal loss during cycling.

Tuning the Electrochemical Reactivity of Boron- and Nitrogen-Substituted Graphene.

The structural modification of nanomaterials at the atomic level has the potential to generate tailor-made components with enhanced performance for a variety of tasks. The chemical versatility of graphene has been constantly employed to fabricate multi-functional doped 2D materials with applications encompassing energy storage and electrocatalysis. Despite the many reports on boron- and nitrogen-doped graphenes, the possible synergy that arises from combining these electronically complementary elements has yet to be fully understood and explored. The techniques used for the fabrication of these nanomaterials are reviewed, along with the most recent reports on the benefits of B, N singly doping and co-doping in the electrocatalysis for oxygen reduction reactions and for energy storage in supercapacitors and lithium secondary batteries. The investigation of bulk co-doped materials has intrinsic limitations in fully understanding the real role of heteroatoms in the above applications. Ultimately, the design and creation of substituted monolayers with controlled compositions might hold the key for carbon-based energy-related applications.

Quasi-Solid Electrolytes for High Temperature Lithium Ion Batteries.

Rechargeable batteries capable of operating at high temperatures have significant use in various targeted applications. Expanding the thermal stability of current lithium ion batteries requires replacing the electrolyte and separators with stable alternatives. Since solid-state electrolytes do not have a good electrode interface, we report here the development of a new class of quasi-solid-state electrolytes, which have the structural stability of a solid and the wettability of a liquid. Microflakes of clay particles drenched in a solution of lithiated room temperature ionic liquid forming a quasi-solid system has been demonstrated to have structural stability until 355 °C. With an ionic conductivity of ∼3.35 mS cm(-1), the composite electrolyte has been shown to deliver stable electrochemical performance at 120 °C, and a rechargeable lithium battery with Li4Ti5O12 electrode has been tested to deliver reliable capacity for over several cycles of charge-discharge.

Supercapacitor operating at 200 degrees celsius.

The operating temperatures of current electrochemical energy storage devices are limited due to electrolyte degradation and separator instability at higher temperatures. Here we demonstrate that a tailored mixture of materials can facilitate operation of supercapacitors at record temperatures, as high as 200°C. Composite electrolyte/separator structures made from naturally occurring clay and room temperature ionic liquids, with graphitic carbon electrodes, show stable supercapacitor performance at 200°C with good cyclic stability. Free standing films of such high temperature composite electrolyte systems can become versatile functional membranes in several high temperature energy conversion and storage applications.

Fast vortex-assisted self-assembly of carbon nanoparticles on an air-water interface.

In this work a self-assembly technique is presented, allowing the fast formation of carbon black thin films. It consists in the controlled addition of a stable carbon material's dispersion over the water surface, disturbed by a vortex. The vortex, although not essential for the film formation, was found to drastically improve film homogeneity. A physical chemical study concerning how several parameters could be used to tune film properties was also conducted. The self-assembled films, which can be picked up in any hydrophilic substrate, showed a good electrical conductivity and a high optical transparency. As an application example, films about 200 nm thick were employed as supercapacitor electrodes.