Betar M. Gallant

High-power lithium batteries from functionalized carbon-nanotube electrodes

Energy storage devices that can deliver high powers have many applications, including hybrid vehicles and renewable energy. Much research has focused on increasing the power output of lithium batteries by reducing lithium-ion diffusion distances, but outputs remain far below those of electrochemical capacitors and below the levels required for many applications. Here, we report an alternative approach based on the redox reactions of functional groups on the surfaces of carbon nanotubes. Layer-by-layer techniques are used to assemble an electrode that consists of additive-free, densely packed and functionalized multiwalled carbon nanotubes. The electrode, which is several micrometres thick, can store lithium up to a reversible gravimetric capacity of approximately 200 mA h g(-1)(electrode) while also delivering 100 kW kg(electrode)(-1) of power and providing lifetimes in excess of thousands of cycles, both of which are comparable to electrochemical capacitor electrodes. A device using the nanotube electrode as the positive electrode and lithium titanium oxide as a negative electrode had a gravimetric energy approximately 5 times higher than conventional electrochemical capacitors and power delivery approximately 10 times higher than conventional lithium-ion batteries.

Lithium–oxygen batteries: bridging mechanistic understanding and battery performance

Rechargeable energy storage systems with high energy density and round-trip efficiency are urgently needed to capture and deliver renewable energy for applications such as electric transportation. Lithium–air/lithium–oxygen (Li–O2) batteries have received extraordinary research attention recently owing to their potential to provide positive electrode gravimetric energies considerably higher (∼3 to 5×) than Li-ion positive electrodes, although the packaged device energy density advantage will be lower (∼2×). In light of the major technological challenges of Li–O2 batteries, we discuss current understanding developed in non-carbonate electrolytes of Li–O2 redox chemistry upon discharge and charge, oxygen reduction reaction product characteristics upon discharge, and the chemical instability of electrolytes and carbon commonly used in the oxygen electrode. We show that the kinetics of oxygen reduction reaction are influenced by catalysts at small discharge capacities (Li2O2 thickness less than ∼1 nm), but not at large Li2O2 thicknesses, yielding insights into the governing processes during discharge. In addition, we discuss the characteristics of discharge products (mainly Li2O2) including morphological, electronic and surface features and parasitic reactivity with carbon. On charge, we examine the reaction mechanism of the oxygen evolution reaction from Li2O2 and the influence of catalysts on bulk Li2O2 decomposition. These analyses provide insights into major discrepancies regarding Li–O2 charge kinetics and the role of catalyst. In light of these findings, we highlight open questions and challenges in the Li–O2 field relevant to developing practical, reversible batteries that achieve the anticipated energy density advantage with a long cycle life.

All-carbon-nanofiber electrodes for high-energy rechargeable Li–O2 batteries

Hollow carbon fibers with diameters on the order of 30 nm were grown on a ceramic porous substrate, which was used as the oxygen electrode in lithium-oxygen (Li–O2) batteries. These all-carbon-fiber (binder-free) electrodes were found to yield high gravimetric energies (up to 2500 W h kgdischarged−1) in Li–O2cells, translating to an energy enhancement ∼4 times greater than the state-of-the-art lithium intercalation compounds such as LiCoO2 (∼600 W h kgelectrode−1). The high gravimetric energy achieved in this study can be attributed to low carbon packing in the grown carbon-fiber electrodes and highly efficient utilization of the available carbon mass and void volume for Li2O2 formation. The nanofiber structure allowed for the clear visualization of Li2O2 formation and morphological evolution during discharge and its disappearance upon charge, where Li2O2 particles grown on the sidewalls of the aligned carbon fibers were found to be toroids, having particle sizes increasing (up to ∼1 μm) with increasing depth-of-discharge. The visualization of Li2O2 morphologies upon discharge and disappearance upon charge represents a critical step toward understanding key processes that limit the rate capability and low round-trip efficiencies of Li–O2 batteries, which are not currently understood within the field.

Nanostructured carbon-based electrodes: bridging the gap between thin-film lithium-ion batteries and electrochemical capacitors

The fast evolution of portable electronic devices and micro-electro-mechanical systems (MEMS) requires multi-functional microscale energy sources that have high power, high energy, long cycle life, and the adaptability to various substrates. Nanostructured thin-film lithium-ion batteries and electrochemical capacitors (ECs) are among the most promising energy storage devices that can meet these demands. This perspective presents an overview of recent progresses and challenges associated with the development of binder-free, carbon-based nanostructured electrodes prepared from layer-by-layer (LbL) electrostatic assembly, which provide enhanced gravimetric and volumetric energy for ECs and enhanced power capabilities for batteries. Based on promising findings for thin electrodes of several microns in thickness, LbL-based electrodes could also potentially be envisioned for portable electronics, electrified transportation, and load-leveling applications if successful scale-up to tens or hundreds of microns can be achieved.

Influence of Li2O2 morphology on oxygen reduction and evolution kinetics in Li–O2 batteries

Understanding the origins of high overpotentials required for Li2O2 oxidation in Li–O2 batteries is critical for developing practical devices with improved round-trip efficiency. While a number of studies have reported different Li2O2 morphologies formed during discharge, the influence of the morphology and structure of Li2O2 on the oxygen evolution reaction (OER) kinetics and pathways is not known. Here, we show that two characteristic Li2O2 morphologies are formed in carbon nanotube (CNT) electrodes in a 1,2-dimethoxyethane (DME) electrolyte: discs/toroids (50–200 nm) at low rates/overpotentials (10 mA gC−1 or E > 2.7 V vs. Li), or small particles (<20 nm) at higher rates/overpotentials. Upon galvanostatic charging, small particles exhibit a sloping profile with low overpotential (<4 V) while discs exhibit a two-stage process involving an initially sloping region followed by a voltage plateau. Potentiostatic intermittent titration technique (PITT) measurements reveal that charging in the sloping region corresponds to solid solution-like delithiation, whereas the voltage plateau (E = 3.4 V vs. Li) corresponds to two-phase oxidation. The marked differences in charging profiles are attributed to differences in surface structure, as supported by X-ray absorption near edge structure (XANES) data showing that oxygen anions on disc surfaces have LiO2-like electronic features while those on the particle surfaces are more bulk Li2O2-like with modified electronic structure compared to commercial Li2O2. Such an integrated structural, chemical, and morphological approach to understanding the OER kinetics provides new insights into the desirable discharge product structure for charging at lower overpotentials.

Mechanisms of Morphological Evolution of Li2O2 Particles during Electrochemical Growth

Li-O2 batteries, wherein solid Li2O2 is formed at the porous air cathode during discharge, are candidates for high gravimetric energy (3212 Wh/kgLi2O2) storage for electric vehicles. Understanding and controlling the nucleation and morphological evolution of Li2O2 particles upon discharge is key to achieving high volumetric energy densities. Scanning and transmission electron microscopy were used to characterize the discharge product formed in Li-O2 batteries on electrodes composed of carpets of aligned carbon nanotubes. At low discharge rates, Li2O2 particles form first as stacked thin plates, ∼10 nm in thickness, which spontaneously splay so that secondary nucleation of new plates eventually leads to the development of a particle with a toroidal shape. Li2O2 crystallites have large (001) crystal faces consistent with the theoretical Wulff shape and appear to grow by a layer-by-layer mechanism. In contrast, at high discharge rates, copious nucleation of equiaxed Li2O2 particles precedes growth of discs and toroids.

In Situ Transmission Electron Microscopy Observations of Electrochemical Oxidation of Li2O2

In this Letter, we report the first in situ transmission electron microscopy observation of electrochemical oxidation of Li2O2, providing insights into the rate limiting processes that govern charge in Li-O2 cells. In these studies, oxidation of electrochemically formed Li2O2 particles, supported on multiwall carbon nanotutubes (MWCNTs), was found to occur preferentially at the MWCNT/Li2O2 interface, suggesting that electron transport in Li2O2 ultimately limits the oxidation kinetics at high rates or overpotentials.

Rate-Dependent Morphology of Li2O2 Growth in Li–O2 Batteries

Compact solid discharge products enable energy storage devices with high gravimetric and volumetric energy densities, but solid deposits on active surfaces can disturb charge transport and induce mechanical stress. In this Letter, we develop a nanoscale continuum model for the growth of Li2O2 crystals in lithium-oxygen batteries with organic electrolytes, based on a theory of electrochemical nonequilibrium thermodynamics originally applied to Li-ion batteries. As in the case of lithium insertion in phase-separating LiFePO4 nanoparticles, the theory predicts a transition from complex to uniform morphologies of Li2O2 with increasing current. Discrete particle growth at low discharge rates becomes suppressed at high rates, resulting in a film of electronically insulating Li2O2 that limits cell performance. We predict that the transition between these surface growth modes occurs at current densities close to the exchange current density of the cathode reaction, consistent with experimental observations.

Self-standing positive electrodes of oxidized few-walled carbon nanotubes for light-weight and high-power lithium batteries

Binder-free and self-standing carbon nanotube (CNT) electrodes of tens of microns in thickness have been assembled via a vacuum-filtration process of oxidized few-walled CNTs (FWNTs), with different amounts of oxygen functional groups on FWNTs. Sub-millimetre long FWNTs can provide high electrical conductivity and mechanical strength in self-standing porous networks by reducing the number of junctions among FWNTs. We show that the gravimetric capacity of FWNT electrodes in lithium cells can be enhanced by increasing oxygen functional groups on FWNTs, which results from Faradaic reactions between lithium ions and surface oxygen functional groups. These self-standing FWNT electrodes (free of binder/additive and current collector) can provide a high gravimetric energy of ∼200 W h kg−1 at a high power of ∼10 kW kg−1, showing promise as the positive electrode for light-weight, high-power lithium batteries.

Synthesis of Highly Stable Sub-8 nm TiO2 Nanoparticles and Their Multilayer Electrodes of TiO2/MWNT for Electrochemical Applications

Next-generation electrochemical energy storage for integrated microsystems and consumer electronic devices requires novel electrode materials with engineered architectures to meet the requirements of high performance, low cost, and robustness. However, conventional electrode fabrication processes such as doctor blading afford limited control over the electrode thickness and structure at the nanoscale and require the incorporation of insulating binder and other additives, which can promote agglomeration and reduce active surface area, limiting the inherent advantages attainable from nanoscale materials. We have engineered a route for the synthesis of highly stable, sub-8 nm TiO2 nanoparticles and their subsequent incorporation with acid-functionalized multiwalled carbon nanotubes (MWNTs) into nanostructured electrodes using aqueous-based layer-by-layer electrostatic self-assembly. Using this approach, binder-free thin film electrodes with highly controllable thicknesses up to the micrometer scale were developed with well-dispersed, nonagglomerated TiO2 nanoparticles on MWNTs. Upon testing in an Li electrochemical half-cell, these electrodes demonstrate high capacity (>150 mAh/gel(ectrode) at 0.1 A/gel(ectrode)), good rate capability (>100 mAh/gel(ectrode) up to 1 A/g(electrode)) and nearly no capacity loss up to 200 cycles for electrodes with thicknesses up to 1480 nm, indicating their promise as thin-film negative electrodes for future Li storage applications.