A high-performance solid-state lithium-oxygen battery with a ceramic-carbon nanostructured electrode (original) (raw)
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A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries
Nature Communications, 2013
The lithium-oxygen battery, of much interest because of its very high-energy density, presents many challenges, one of which is a high-charge overpotential that results in large inefficiencies. Here we report a cathode architecture based on nanoscale components that results in a dramatic reduction in charge overpotential to B0.2 V. The cathode utilizes atomic layer deposition of palladium nanoparticles on a carbon surface with an alumina coating for passivation of carbon defect sites. The low charge potential is enabled by the combination of palladium nanoparticles attached to the carbon cathode surface, a nanocrystalline form of lithium peroxide with grain boundaries, and the alumina coating preventing electrolyte decomposition on carbon. High-resolution transmission electron microscopy provides evidence for the nanocrystalline form of lithium peroxide. The new cathode material architecture provides the basis for future development of lithium-oxygen cathode materials that can be used to improve the efficiency and to extend cycle life.
Chemistry of Materials, 2012
The high capacity of the layered Li−excess oxide cathode is always accompanied by extraction of a significant amount of oxygen from the structure. The effects of oxygen on the electrochemical cycling are not well understood. Here, the detailed reaction scheme following oxygen evolution was established using real-time gas analysis and ex situ chemical analysis of the surface of the electrodes. A series of electrochemical/chemical reactions involving oxygen radicals constantly produced and decomposed lithium carbonate during cell operation. Moreover, byproducts, including water, affected the cycle life and rate capability: hydrolysis of the electrolyte salt formed hydrofluoric acid that attacked the surface of the electrode. This finding implies that protection of the electrode surface from damage, for example, by a coating or removal of oxygen radicals by scavengers, will be critical to widespread usage of Li−excess transition metal oxides in rechargeable lithium batteries.
Porous Titanium Oxide Microspheres as Promising Catalyst for Lithium–Oxygen Batteries
Energy Technology, 2020
Lithium-oxygen (Li-O 2) batteries have received much attention due to the superior theoretical energy density. However, commercialization is still hindered by several challenges including the high charge overpotential and poor cycling stability. Herein, small particle-stacked TiO 2 microspheres are successfully synthesized through a facile hydrolysis and hydrothermal method. Such unique architectures provide 3D framework with more catalytically active sites and rich porosity for the storage of discharge products and oxygen diffusion. Li-O 2 batteries utilizing the TiO 2 microspheres electrode show a much higher specific capacity and a lower overpotential than those with pure carbon nanotube (CNT) electrodes. Moreover, they exhibit an enhanced cycling stability and TiO 2 microspheres show great potential as a promising catalyst for Li-O 2 batteries.
Energy Materials, 2023
Realizing long-life cycling is the biggest challenge in the research field of Li-O2 batteries in the current stage. The main reasons for poor cycling performance are the sluggish Li2O2 formation and decomposition process, as well as the side reaction of carbon cathode. In order to accurately address the problems above, a TiO2 /CNTs cathode was rationally designed for long-life Li-O2 batteries. The CNTs skeleton offers multiple three-dimensional channels for the rapid transportation of oxygen, Li + and electrons. A thin-film and discontinuous layer of TiO2 is coated on the CNTs surface to effectively inhibit the carbon corrosion but still could let mass transfer smoothly. Ultrafine Ru nanoparticles decorating the TiO2 /CNTs serve as efficient catalytic active sites. Benefiting from the unique structure design, Li-O2 batteries with the cathode of TiO2 /CNTs achieve a cycling life of 110 with a fixed capacity of 500 mAh g-1 at a current density of 100 mA g-1. Our research generates new ideas for designing long-cycling Li-O2 battery cathodes.
Low-Overpotential Li–O 2 Batteries Based on TFSI Intercalated Co–Ti Layered Double Oxides
advanced functional materials
Lithium–oxygen batteries with an exceptionally high theoretical energy density have triggered worldwide interest in energy storage system. The research focus of lithium–oxygen batteries lies in the development of catalytic materials with excellent cycling stability and high bifunctional catalytic activity in oxygen reduction and oxygen evolution reactions. Here, a hierarchically porous fl ower-like cobalt–titanium layered double oxide on nickel foam with interca- lated anions of bistrifl uoromethane sulfonamide (TFSI) is designed and pre- pared. When used as a binder-free cathode for lithium–oxygen batteries, this material exhibits low polarization (initial polarization of 0.45 V) and superior cycling stability (80 cycles at a current density of 100 mA g −1 at full discharge/ charge). The high electrochemical performance of the cathode material is attributed to the good dispersion of binary elements in its host layer and good compatibility with lithium bistrifl uoromethane sulfonamide electrolyte induced by intercalated guest anions of TFSI within its interlayer. This work provides a novel strategy for the fabrication of binder-free cathodes based on layered double oxides for high-performance lithium–oxygen batteries.
Solid-state batteries: Unlocking lithium's potential with ceramic solid electrolytes
Recent progress indicates that ceramic materials may soon supplant liquid electrolytes in batteries, offering improved energy capacity and safety. W idespread adoption of electric vehicles (EV) will require dramatic changes to the energy storage market. Total worldwide lithium-ion (Li-ion) battery production was 221 GWh in 2018, while EV demand alone is projected to grow to more than 1,700 GWh by 2030. 1 As economies of scale have been met in Li-ion battery production, price at the pack level has fallen and is expected to break $100/kWh within the next few years. Li-ion batteries are expected to address near-term energy storage needs, with advances in cell chemistry providing steady improvement in cell capacity. Yet Li-ion batteries will eventually approach the practical limits of their energy storage capacity , and the volatile flammable liquid electrolyte in Li-ion cells requires thermal management systems that add cost, mass, and complexity to EV battery packs. Recent progress demonstrates that Li-ion conducting solid electrolytes have fundamental properties to supplant current Li-ion liquid electrolytes. Moreover, using solid electrolytes enables all-solid-state batteries, a new class of lithium batteries that are expected to reach storage capacities well beyond that of today's Li-ion batteries. The promise of a safer high-capacity battery has attracted enormous attention from fundamental research through start-up companies, with significant investment from venture capitalists and automakers. The Li-ion battery The 1970s marked development of the first Li-ion cathode intercalation materials. Cells with a metallic lithium anode were commercialized in the 1980s, but it was soon discovered Solid-state batteries: Unlocking lithium's potential with ceramic solid electrolytes that lithium deposits in dendritic structures upon battery cycling. These dendrites eventually grow through the separa-tor, connecting the anode and cathode and causing a dangerous short circuit of the cell. The solution was to replace the lithium anode with a graphite Li-ion host material, thereby producing the modern Li-ion battery. First introduced by Sony in 1991, the graphite anode is paired with a LiCoO 2 cathode and flooded with a liquid organic electrolyte with dissolved lithium salt. The dissolved lithium provides Li-ion transport within the cell. A thin and porous polymer separator prevents physical contact between the anode and cathode while allowing ionic transport between electrodes. This basic cell structure remains unchanged today, albeit with numerous energy-boosting innovations, including silicon anode additions, electrolyte additives to increase cycle life, and high nickel-content cathodes. These innovations have led to an average of 8% annualized energy density improvement in Li-ion batteries. 2 Despite this progress, the volumetric energy density of Li-ion batteries can only reach a practical limit of about 900 Wh/L at the cell level. For Li-ion batteries, active cathode and anode powders are mixed with binder and cast on a current collector using doctor blade, reverse comma, or slot die coating. These electrodes are slit into desired dimensions, interleaved with a separator, and either wound-as is the case of an 18650 (18 mm diameter; 65 mm length) cylindrical cell-or stacked or folded to produce a prismatic pouch cell. Figure 1 shows 18650 cylindrical wound cells and 10-Ah pouch cells. For EV applications, cells are arranged into modules, which are placed into a battery pack. For example, a Tesla Model 3 contains more than 4,000 individual cylindrical cells, producing about 80 kWh of storage. Other manufacturers , such as GM, use pouch-type cells, with 288 cells producing 60 kWh of storage in the Chevy Bolt. Li-ion battery packs contain significant battery management systems to keep cells within a safe operating range. Heat generated within the pack must be removed by cooling systems to protect both the performance and lifetime of Li-ion cells. Credit: Evan Dougherty/University of Michigan Engineering Communications and Marketing Induction coils heat a die for rapid densification of Li-ion conducting Li 7 La 3 Zr 2 O 12 ceramic solid electrolyte.
Small Methods, 2018
liquid electrolytes (LEs) has brought safety hazards associated with the leakage and flammability of organic LEs, especially in Li-O 2 batteries with an open system. [2] Another intrinsic drawback of using LEs in Li-O 2 batteries is the undesired and inevitable formation of Li dendrites, which is mainly triggered by the inhomogeneous Li ions distribution on the surface of Li metal due to the high electric field near tips (commonly known as "tip effect"). [3] This is a common problem in Li metal batteries. Whether the problem can be resolved properly directly determines the practicality of Li metal. Moreover, the evaporation of LEs and their failure in inhibiting O 2 crossover are also serious concerns that hamper the development of Li-O 2 batteries. [4] In this context, replacing organic LEs with (quasi) solid-state electrolytes (SSEs) is a strategy to overcome these shortcomings and achieve high safety. [5] Among the possible candidates, ceramic SSEs are shown to suppress Li dendrite growth, but most of reported ceramic SSEs feature relatively low ionic conductivity and high interfacial resistance with electrodes, in turn leading to deterioration of electrochemical performance. In particular, the drawbacks would be exacerbated in Li-O 2 batteries which intrinsically feature sluggish electrochemical dynamics. [6] Meanwhile, most ceramic SSEs are chemically unstable against Li metal. [7] Alternatively, polymer SSEs show additional advantages in scalability and processability, but they usually require operation at higher temperatures than room temperature, which will increase the difficulty and complexity of the operation condition and may trigger more side reactions in Li-O 2 batteries. [5c,d,7,8] For the development of safe solid-state Li-O 2 batteries, all these drawbacks need to be overcome. Gel polymer electrolytes (GPEs), combing the high ionic conductivity of LE and the mechanical properties of polymer SSE, have drawn considerable attentions for being used as both electrolyte and separator. [9] Besides, GPEs can render the energy storage devices with adjustable shapes and high flexibility, which is promising for the burgeoning portable and wearable electronics. With these merits, GPEs have been reported to be used in Li-O 2 batteries and show relatively improved Development of Li-O 2 batteries with ultrahigh theoretical energy density is highly desired to meet the ever-increasing demand of energy density. However, safety concerns and cycling life have become main bottlenecks that inhibit the practical applications of Li-O 2 batteries because of the use of organic liquid electrolytes (LEs) and the noneffective air electrodes. Gel polymer electrolytes (GPEs) are reported to be used in Li-O 2 batteries and show relatively improved performance than LEs, but they are still below the expectation. Herein, a quasi-solid-state Li-O 2 battery constructed with a GPE and a high-efficiency air electrode is proposed. Excellent electrochemical performance is demonstrated beyond the batteries with LE, evidenced by the ultralong cycle life of up to 553 cycles and stable operating time for over 1100 h. The elongated cycling life benefits from the role of GPE in blocking O 2 crossover, protecting Li metal, and avoiding electrolyte evaporation compared with LE. It is expected that the present study can shed light on the future study on developing efficient catalysts for (quasi) solid-state Li-O 2 battery. Lithium-Oxygen Batteries