Direct Visualization of Lithium Polysulfides and Their Suppression in Liquid Electrolyte.

Understanding of lithium polysulfide (Li-PS) formation and the shuttle phenomenon is essential for practical application of the lithium/sulfur (Li/S) cell, which has superior theoretical specific energy (2600 Wh/kg). However, it suffers from the lack of direct observation on behaviors of soluble Li-PS in liquid electrolytes. Using in situ graphene liquid cell electron microscopy, we have visualized formation and diffusion of Li-PS simultaneous with morphological and phase evolutions of sulfur nanoparticles during lithiation. We found that the morphological changes and Li-PS diffusion are retarded by ionic liquid (IL) addition into electrolyte. Chronoamperometric shuttle current measurement confirms that IL addition lowers the experimental diffusion coefficient of Li-PS by 2 orders of magnitude relative to that in IL-free electrolyte and thus suppresses the Li-PS shuttle current, which accounts for better cyclability and Coulombic efficiency of the Li/S cell. This study provides significant insights into electrolyte design to inhibit the polysulfide shuttle phenomenon.

Three-Dimensionally Aligned Sulfur Electrodes by Directional Freeze Tape Casting.

Rational design of sulfur electrodes is exceptionally important in enabling a high-performance lithium/sulfur cell. Constructing a continuous pore structure of the sulfur electrode that enables facile lithium ion transport into the electrode and mitigates the reconstruction of sulfur is a key factor for enhancing the electrochemical performance. Here, we report a three-dimensionally (3D) aligned sulfur electrode cast onto conventional aluminum foil by directional freeze tape casting. The 3D aligned sulfur-graphene oxide (S-GO) electrode consisting of few micron thick S-GO layers with 10-20 µm interlayer spacings demonstrates significant improvement in the performance of the Li/S cell. Moreover, the freeze tape cast graphene oxide electrode exhibits homogeneous reconfiguration behavior in the polysulfide catholyte cell tests and demonstrated extended cycling capability with only 4% decay of the specific capacity over 200 cycles. This work emphasizes the critical importance of proper structural design for sulfur-carbonaceous composite electrodes.

Electrochemical Reaction Mechanism of the MoS2 Electrode in a Lithium-Ion Cell Revealed by in Situ and Operando X-ray Absorption Spectroscopy.

As a typical transition metal dichalcogenide, MoS2 offers numerous advantages for nanoelectronics and electrochemical energy storage due to its unique layered structure and tunable electronic properties. When used as the anode in lithium-ion cells, MoS2 undergoes intercalation and conversion reactions in sequence upon lithiation, and the reversibility of the conversion reaction is an important but still controversial topic. Here, we clarify unambiguously that the conversion reaction of MoS2 is not reversible, and the formed Li2S is converted to sulfur in the first charge process. Li2S/sulfur becomes the main redox couple in the subsequent cycles and the main contributor to the reversible capacity. In addition, due to the insulating nature of both Li2S and sulfur, a strong relaxation effect is observed during the cycling process. This study clearly reveals the electrochemical lithiation-delithiation mechanism of MoS2, which can facilitate further developments of high-performance MoS2-based electrodes.

Tracking the Chemical and Structural Evolution of the TiS2 Electrode in the Lithium-Ion Cell Using Operando X-ray Absorption Spectroscopy.

As the lightest and cheapest transition metal dichalcogenide, TiS2 possesses great potential as an electrode material for lithium batteries due to the advantages of high energy density storage capability, fast ion diffusion rate, and low volume expansion. Despite the extensive investigation of its electrochemical properties, the fundamental discharge-charge reaction mechanism of the TiS2 electrode is still elusive. Here, by a combination of ex situ and operando X-ray absorption spectroscopy with density functional theory calculations, we have clearly elucidated the evolution of the structural and chemical properties of TiS2 during the discharge-charge processes. The lithium intercalation reaction is highly reversible and both Ti and sulfur are involved in the redox reaction during the discharge and charge processes. In contrast, the conversion reaction of TiS2 is partially reversible in the first cycle. However, Ti-O related compounds are developed during electrochemical cycling over extended cycles, which results in the decrease of the conversion reaction reversibility and the rapid capacity fading. In addition, the solid electrolyte interphase formed on the electrode surface is found to be highly dynamic in the initial cycles and then gradually becomes more stable upon further cycling. Such understanding is important for the future design and optimization of TiS2 based electrodes for lithium batteries.

Revealing the Electrochemical Charging Mechanism of Nanosized Li2S by in Situ and Operando X-ray Absorption Spectroscopy.

Lithium sulfide (Li2S) is a promising cathode material for lithium-sulfur (Li/S) cells due to its high theoretical specific capacity (1166 mAh g-1) and ability to pair with nonmetallic lithium anodes to avoid potential safety issues. However, when used as the cathode, a high charging voltage (∼4 V versus Li+/Li) is always necessary to activate Li2S in the first charge process, and the voltage profile becomes similar to that of a common sulfur electrode in the following charge processes. In this report, we have prepared an electrode of nanosphere Li2S particles and investigated its charging mechanism of the initial two charge processes by in situ and operando X-ray absorption spectroscopy. The results indicate that Li2S is directly converted to elemental sulfur through a two-phase transformation in the first charge process, while it is oxidized first to polysulfides and then to sulfur in the second charge process. The origin of the different charging mechanisms and corresponding charge-voltage profiles of the first and second charge processes is found to be related to the remaining polysulfides at the end of the first discharge process: they can not only facilitate the charge-transfer process at the Li2S/electrolyte interface but also chemically react with Li2S and act as the polysulfide facilitator for the electrochemical oxidation of Li2S in the following charge processes. Our present study provides a new fundamental understanding of the charging mechanism of the Li2S electrode, which should be of help for the further development of high-performance Li/S cells.

Freeze-Dried Sulfur-Graphene Oxide-Carbon Nanotube Nanocomposite for High Sulfur-Loading Lithium/Sulfur Cells.

The ambient-temperature rechargeable lithium/sulfur (Li/S) cell is a strong candidate for the beyond lithium ion cell since significant progress on developing advanced sulfur electrodes with high sulfur loading has been made. Here we report on a new sulfur electrode active material consisting of a cetyltrimethylammonium bromide-modified sulfur-graphene oxide-carbon nanotube (S-GO-CTA-CNT) nanocomposite prepared by freeze-drying. We show the real-time formation of nanocrystalline lithium sulfide (Li2S) at the interface between the S-GO-CTA-CNT nanocomposite and the liquid electrolyte by in situ TEM observation of the reaction. The combination of GO and CNT helps to maintain the structural integrity of the S-GO-CTA-CNT nanocomposite during lithiation/delithiation. A high S loading (11.1 mgS/cm2, 75% S) S-GO-CTA-CNT electrode was successfully prepared using a three-dimensional structured Al foam as a substrate and showed good S utilization (1128 mAh/g S corresponding to 12.5 mAh/cm2), even with a very low electrolyte to sulfur weight ratio of 4. Moreover, it was demonstrated that the ionic liquid in the electrolyte improves the Coulombic efficiency and stabilizes the morphology of the Li metal anode.

Lithium Sulfide (Li2S)/Graphene Oxide Nanospheres with Conformal Carbon Coating as a High-Rate, Long-Life Cathode for Li/S Cells.

In recent years, lithium/sulfur (Li/S) cells have attracted great attention as a candidate for the next generation of rechargeable batteries due to their high theoretical specific energy of 2600 W·h kg(-1), which is much higher than that of Li ion cells (400-600 W·h kg(-1)). However, problems of the S cathode such as highly soluble intermediate species (polysulfides Li2Sn, n = 4-8) and the insulating nature of S cause poor cycle life and low utilization of S, which prevents the practical use of Li/S cells. Here, a high-rate and long-life Li/S cell is proposed, which has a cathode material with a core-shell nanostructure comprising Li2S nanospheres with an embedded graphene oxide (GO) sheet as a core material and a conformal carbon layer as a shell. The conformal carbon coating is easily obtained by a unique CVD coating process using a lab-designed rotating furnace without any repetitive steps. The Li2S/GO@C cathode exhibits a high initial discharge capacity of 650 mA·h g(-1) of Li2S (corresponding to the 942 mA·h g(-1) of S) and very low capacity decay rate of only 0.046% per cycle with a high Coulombic efficiency of up to 99.7% for 1500 cycles when cycled at the 2 C discharge rate.

Durable carbon-coated Li2(S) core-shell spheres for high performance lithium/sulfur cells.

Lithium sulfide (Li2S) is an attractive cathode material with a high theoretical specific capacity (1166 mAh g(-1)). However, the poor cycle life and rate capability have remained significant challenges, preventing its practical application. Here, Li2S spheres with size control have been synthesized for the first time, and a CVD method for converting them into stable carbon-coated Li2S core-shell (Li2S@C) particles has been successfully employed. These Li2S@C particles with protective and conductive carbon shells show promising specific capacities and cycling performance with a high initial discharge capacity of 972 mAh g(-1) Li2S (1394 mAh g(-1) S) at the 0.2C rate. Even with no added carbon, a very high Li2S content (88 wt % Li2S) electrode composed of 98 wt % 1 µm Li2S@C spheres and 2 wt % binder shows rather stable cycling performance, and little morphology change after 400 cycles at the 0.5C rate.

Understanding the degradation mechanism of rechargeable lithium/sulfur cells: a comprehensive study of the sulfur-graphene oxide cathode after discharge-charge cycling.

Lithium/sulfur (Li/S) cells have attracted much attention due to their higher theoretical specific capacity and energy compared to those of current lithium-ion cells. However, the application of Li/S cells is still hampered by short cycle life. Sulfur-graphene oxide (S-GO) nanocomposites have shown promise as cathode materials for long-life Li/S cells because oxygen-containing functional groups on the surface of graphene oxide were successfully used as sulfur immobilizers by forming weak bonds with sulfur and polysulfides. While S-GO showed much improved cycling performance, the capacity decay still needs to be improved for commercially viable cells. In this study, we attempt to understand the capacity fading mechanism based on an ex situ study of the structural and chemical evolution of S-GO nanocomposite cathodes with various numbers of cycles using scanning electron microscopy (SEM), near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS). It is found that both the surface morphologies and chemical structures of the cathode materials change considerably with increasing number of cycles. These changes are attributed to several unexpected chemical reactions of lithium with S-GO nanocomposites occurring during the discharge-charge processes with the formation of Li2CO3, Li2SO3, Li2SO4, and COSO2Li species. These reactions result in the loss of recyclable active sulfur on the surface of the electrode, and thus capacity fades while coulombic efficiency is near 100%. Moreover, the reaction products accumulate on the cathode surface, forming a compact blocking insulating layer which may make the diffusion of Li ions into/out of the cathode difficult during the discharge-charge process and thus lead to lower utilization of sulfur at higher rates. We think that these two observations are significant contributors to the capacity and rate capability degradation of the Li/S-GO cells. Therefore, for the rechargeable Li/S-GO cells, we suggest that the content of oxygen-containing functional groups on GO should be optimized and more stable functional groups need to be identified for further improvement of the cycling performance. The information we gain from this study may provide general insights into the fundamental understanding of the degradation mechanisms of other rechargeable Li/S cells using similar oxygen-containing functional groups as sulfur immobilizers.

A long-life, high-rate lithium/sulfur cell: a multifaceted approach to enhancing cell performance.

Lithium/sulfur (Li/S) cells are receiving significant attention as an alternative power source for zero-emission vehicles and advanced electronic devices due to the very high theoretical specific capacity (1675 mA·h/g) of the sulfur cathode. However, the poor cycle life and rate capability have remained a grand challenge, preventing the practical application of this attractive technology. Here, we report that a Li/S cell employing a cetyltrimethyl ammonium bromide (CTAB)-modified sulfur-graphene oxide (S-GO) nanocomposite cathode can be discharged at rates as high as 6C (1C = 1.675 A/g of sulfur) and charged at rates as high as 3C while still maintaining high specific capacity (~ 800 mA·h/g of sulfur at 6C), with a long cycle life exceeding 1500 cycles and an extremely low decay rate (0.039% per cycle), perhaps the best performance demonstrated so far for a Li/S cell. The initial estimated cell-level specific energy of our cell was ~ 500 W·h/kg, which is much higher than that of current Li-ion cells (~ 200 W·h/kg). Even after 1500 cycles, we demonstrate a very high specific capacity (~ 740 mA·h/g of sulfur), which corresponds to ~ 414 mA·h/g of electrode: still higher than state-of-the-art Li-ion cells. Moreover, these Li/S cells with lithium metal electrodes can be cycled with an excellent Coulombic efficiency of 96.3% after 1500 cycles, which was enabled by our new formulation of the ionic liquid-based electrolyte. The performance we demonstrate herein suggests that Li/S cells may already be suitable for high-power applications such as power tools. Li/S cells may now provide a substantial opportunity for the development of zero-emission vehicles with a driving range similar to that of gasoline vehicles.

Nanostructured Li2S-C composites as cathode material for high-energy lithium/sulfur batteries.

With a theoretical capacity of 1166 mA·h·g(-1), lithium sulfide (Li(2)S) has received much attention as a promising cathode material for high specific energy lithium/sulfur cells. However, the insulating nature of Li(2)S prevents the achievement of high utilization (or high capacity) and good rate capability. Various efforts have been made to ameliorate this problem by improving the contact between Li(2)S and electronic conductors. In the literature, however, a relatively high capacity was only obtained with the Li(2)S content below 50 wt %; therefore, the estimated cell specific energy values are often below 350 W·h·kg(-1), which is insufficient to meet the ever-increasing requirements of newly emerging technologies. Here, we report a cost-effective way of preparing nanostructured Li(2)S-carbon composite cathodes by high-energy dry ball milling of commercially available micrometer-sized Li(2)S powder together with carbon additives. A simple but effective electrochemical activation process was used to dramatically improve the utilization and reversibility of the Li(2)S-C electrodes, which was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy. We further improved the cycling stability of the Li(2)S-C electrodes by adding multiwalled carbon nanotubes to the nanocomposites. With a very high specific capacity of 1144 mA·h·g(-1) (98% of the theoretical value) obtained at a high Li(2)S content (67.5 wt %), the estimated specific energy of our cell was ∼610 W·h·kg(-1), which is the highest demonstrated so far for the Li/Li(2)S cells. The cells also maintained good rate capability and improved cycle life. With further improvement in capacity retention, nanostructured Li(2)S-C composite cathodes may offer a significant opportunity for the development of rechargeable cells with a much higher specific energy.

SnS2 nanoparticle loaded graphene nanocomposites for superior energy storage.

SnS2 nanoparticle-loaded graphene nanocomposites were synthesized via one-step hydrothermal reaction. Their electrochemical performance was evaluated as the anode for rechargeable lithium-ion batteries after thermal treatment in an Ar environment. The electrochemical testing results show a high reversible capacity of more than 800 mA h g(-1) at 0.1 C rate and 200 mA h g(-1) for up to 5 C rate. The cells also exhibit excellent capacity retention for up to 90 cycles even at a high rate of 2 C. This electrochemical behavior can be attributed to the well-defined morphology and nanostructures of these as-synthesized nanocomposites, which is characterized by high-resolution transmission electron microscopy and electron energy-loss spectroscopy.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells.

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Here, we use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach enabled us to obtain a uniform and thin (around tens of nanometers) sulfur coating on graphene oxide sheets by a simple chemical reaction-deposition strategy and a subsequent low-temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides enabled us to demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mA h g(-1), and stable cycling for more than 50 deep cycles at 0.1C (1C = 1675 mA g(-1)).

Effects of Photochemical Oxidation of the Carbonaceous Additives on Li-S Cell Performance.

We introduce a simple and easy way to functionalize the surface of various carbonaceous materials through the ultraviolet light/ozone (UV/O3) plasma where we utilize the zero-, one-, and two-dimensional carbon frameworks. In a general manner, the lamps of a UV/O3 generator create two different wavelengths (λ = 185 and 254 nm); the shorter wavelength (λ = 185 nm) dissociates the oxygen (O2) in air and the longer wavelength (λ = 254 nm) dissociates the O3 and creates the reactive and monoatomic oxygen radical, which tends to incorporate onto the defects of the carbons. By tailoring the association and dissociation of the oxygen with various forms, carbon black, carbon nanofibers, and graphite flakes, chosen as representative models for the zero-, one-, and two-dimensional carbon frameworks, their structure can be oxidized, respectively, which is known as photochemical oxidation. Various carbons have their own distinctive morphology and electron transport properties, which are applicable for the lithium-sulfur (Li-S) cell. We, here, report on the improvement of electrochemical performance of the lithium/sulfur cell through such an efficient functionalization approach.

X-ray Absorption Spectroscopy Characterization of a Li/S Cell.

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We have investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N⁺(CH3)3Br-) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. A modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.

A Conversation with Adam Heller.

Adam Heller, Ernest Cockrell Sr. Chair in Engineering Emeritus of the John J. McKetta Department of Chemical Engineering at The University of Texas at Austin, recalls his childhood in the Holocaust and his contributions to science and technology that earned him the US National Medal of Technology and Innovation in a conversation with Elton J. Cairns, Professor of Chemical and Biomolecular Engineering at the University of California, Berkeley. Dr. Heller, born in 1933, describes the enslavement of his father by Hungarians in 1942; the confiscation of his family's home, business, and all its belongings in 1944; and his incarceration in a brick factory with 18,000 Jews who were shipped by the Hungarians to be gassed by Germans in Auschwitz. Dr. Heller and his immediate family survived the Holocaust and arrived in Israel in 1945. He studied under Ernst David Bergmann at the Hebrew University, and then worked at Bell Laboratories and GTE Laboratories, where he headed Bell Lab's Electronic Materials Research Department. At GTE Laboratories, he built in 1966 the first neodymium liquid lasers and in 1973 with Jim Auborn conceived and engineered the lithium thionyl chloride battery, one of the first to be manufactured lithium batteries, which is still in use. After joining the faculty of engineering of The University of Texas at Austin, he cofounded with his son Ephraim Heller TheraSense, now a major part of Abbott Diabetes Care, which produced a microcoulometer that made the monitoring of glucose painless by accurately measuring the blood glucose concentration in 300 nL of blood. He also describes the electrical wiring of enzymes, the basis for Abbott's state-of-the-art continuous glucose monitoring system. He discusses his perspective of reducing the risk of catastrophic global warming in a wealth-accumulating, more-energy-consuming world and provides advice for students entering careers in science or engineering.

Lithium/sulfur batteries with high specific energy: old challenges and new opportunities.

In this review, we begin with a brief discussion of the operating principles and scientific/technical challenges faced by the development of lithium/sulfur cells. We then introduce some recent progress in exploring cathodes, anodes, and electrolytes for lithium/sulfur cells. In particular, several effective strategies used to enhance energy/power density, obtain good efficiencies, and prolong cycle life will be highlighted. We also discuss recent advancements in techniques for investigating electrode reactions in real time and monitoring structural/morphological changes of electrode materials under cell operating conditions to gain a better understanding of the mechanistic details of electrode processes. Finally, the opportunities and perspective for future research directions will be discussed.

Batteries for electric and hybrid-electric vehicles.

Batteries have powered vehicles for more than a century, but recent advances, especially in lithium-ion (Li-ion) batteries, are bringing a new generation of electric-powered vehicles to the market. Key barriers to progress include system cost and lifetime, and derive from the difficulty of making a high-energy, high-power, and reversible electrochemical system. Indeed, although humans produce many mechanical and electrical systems, the number of reversible electrochemical systems is very limited. System costs may be brought down by using cathode materials less expensive than those presently employed (e.g., sulfur or air), but reversibility will remain a key challenge. Continued improvements in the ability to synthesize and characterize materials at desired length scales, as well as to use computations to predict new structures and their properties, are facilitating the development of a better understanding and improved systems. Battery research is a fascinating area for development as well as a key enabler for future technologies, including advanced transportation systems with minimal environmental impact.

An effective stochastic excitation strategy for finding elusive NMR signals from solids.

The versatility of using a stochastic pulse sequence to elucidate peaks with a wide range of shifts, peak widths, and T(1) relaxation times is demonstrated. A stochastic sequence is combined with high speed magic angle spinning (MAS) to obtain the broad and largely shifted peak associated with (31)P in LiNiPO(4). A stochastic sequence is also used to obtain a spectrum of 85% H(3)PO(4), which has a much longer T(1) value. The signal-to-noise was comparable for spectra of 85% H(3)PO(4) obtained with either a stochastic sequence or an optimized Ernst angle experiment. Experimental parameters for the stochastic experiment are set depending only on the ringdown of the probe and not on any inherent qualities of the sample. A stochastic sequence, therefore, combined with MAS provides a useful strategy for finding peaks with unknown T(1) relaxation constants, peak widths, and shifts.

X-ray absorption spectroscopy study of the LixFePO4 cathode during cycling using a novel electrochemical in situ reaction cell.

The extraction and insertion of lithium in LiFePO4 has been investigated in practical Li-ion intercalation electrodes for Li-ion batteries using Fe K-edge X-ray absorption spectroscopy (XAS). A versatile electrochemical in situ reaction cell was utilized, specifically designed for long-term X-ray experiments on battery electrodes during the lithium-extraction/insertion process in electrode materials for Li-ion batteries. The electrode contained about 7.7 mg of LiFePO4 on a 20 microm-thick Al foil. In order to determine the charge compensation mechanism and structural perturbations occurring in the system during cycling, in situ X-ray absorption fine-structure spectroscopy (XAFS) measurements were conducted on the cell at a moderate rate using typical Li-ion battery operating voltages (3.0-4.1 V versus Li/Li+). XAS studies of the LiFePO4 electrode measured at the initial state (LiFePO4) showed iron to be in the Fe(II) state corresponding to the initial state (0.0 mAh) of the battery, whereas in the delithiated state (FePO4) iron was found to be in the Fe(III) state corresponding to the final charged state (3 mAh) of the battery. The X-ray absorption near-edge structure (XANES) region of the XAS spectra revealed a high-spin configuration for the two states [Fe(II), d6 and Fe(III), d5]. The XAFS data analysis confirmed that the olivine structure of the LiFePO4 and FePO4 is retained by the electrodes, which is in agreement with the X-ray diffraction observations on these compounds. The XAFS data that were collected continuously during cycling revealed details about the response of the cathode to Li insertion and extraction. These measurements on the LiFePO4 cathode show that the material retains good structural short-range order leading to superior cycling.