Project description:Lithium-ion batteries have received significant research interest due to their advantages in energy and power density, which are important to enabling many devices. One route to further increase energy density is to fabricate thicker electrodes in the battery cell; however, careful consideration must be taken when designing electrodes as to how increasing the thickness impacts the multiscale and multiphase molecular transport processes, which can limit the overall battery operating power. Design of these electrodes necessitates probing the molecular processes when the battery cell undergoes electrochemical charge/discharge. One tool for in situ insights into the cell is neutron imaging, because neutron imaging can provide information of where electrochemical processes occur within the electrodes. In this manuscript, neutron imaging is applied to track the lithiation/delithiation processes within electrodes at different current densities for a full cell with a thick sintered Li4Ti5O12 anode and LiCoO2 cathode. The neutron imaging reveals that the molecular distribution of Li+ during discharge within the electrode is sensitive to the current density, or equivalently discharge rate. An electrochemical model provides additional insights into the limiting processes occurring within the electrodes. In particular, the impact of tortuosity and molecular transport in the liquid phase within the interstitial regions in the electrodes are considered, and the influence of tortuosity was shown to be highly sensitive to the current density. Qualitatively, the experimental results suggest that the electrodes behave consistent with the packed hard sphere approximation of Bruggeman tortuosity scaling, which indicates that the electrodes are largely mechanically intact but also that a design that incorporates tunable tortuosity could improve the performance of these types of electrodes.
Project description:Quinones, which are ubiquitous in nature, can act as sustainable and green electrode materials but face dissolution in organic electrolytes, resulting in fast fading of capacity and short cycle life. We report that quinone electrodes, especially calix[4]quinone (C4Q) in rechargeable metal zinc batteries coupled with a cation-selective membrane using an aqueous electrolyte, exhibit a high capacity of 335 mA h g-1 with an energy efficiency of 93% at 20 mA g-1 and a long life of 1000 cycles with a capacity retention of 87% at 500 mA g-1. The pouch zinc batteries with a respective depth of discharge of 89% (C4Q) and 49% (zinc anode) can deliver an energy density of 220 Wh kg-1 by mass of both a C4Q cathode and a theoretical Zn anode. We also develop an electrostatic potential computing method to demonstrate that carbonyl groups are active centers of electrochemistry. Moreover, the structural evolution and dissolution behavior of active materials during discharge and charge processes are investigated by operando spectral techniques such as IR, Raman, and ultraviolet-visible spectroscopies. Our results show that batteries using quinone cathodes and metal anodes in aqueous electrolyte are reliable approaches for mass energy storage.
Project description:Driven by expanding interest in battery storage solutions and the success story of lithium-ion batteries, the research for the discovery and optimization of new battery materials and concepts is at peak. The generation of experimental (dis)charge data using coin cells is fast and feasible and proves to be a favorite practice in the battery research labs. The quantitative interpretation of the data, however, is not trivial and decelerates the process of screening and optimization of electrode materials and recipes. Here, we introduce the concept of polarographic map and demonstrate how it can be leveraged to quantify the contribution of different non-equilibrium phenomena to the performance limitation and total polarization of a lithium-ion cell. We showcase the accuracy and diagnostic power of this approach by preparing and analyzing the electrochemical performance of 54 sets of LiNixMnyCo1-x-yO2 electrodes with different formulations and designs discharged in a range of 0.2C-5C.
Project description:Water-in-salt (WIS) electrolytes provide a promising path toward aqueous battery systems with enlarged operating voltage windows for better safety and environmental sustainability. In this work, a new electrode couple, LiV3O8-LiMn2O4, for aqueous Li-ion batteries is investigated to understand the mechanism by which the WIS electrolyte improves the cycling stability at an extended voltage window. Operando synchrotron transmission x-ray microscopy on the LiMn2O4 cathode reveals that the WIS electrolyte suppresses the mechanical damage to the electrode network and dissolution of the electrode particles, in addition to delaying the water decomposition process. Because the viscosity of WIS is notably higher, the reaction heterogeneity of the electrodes is quantified with x-ray absorption spectroscopic imaging, visualizing the kinetic limitations of the WIS electrolyte. This work furthers the mechanistic understanding of electrode-WIS electrolyte interactions and paves the way to explore the strategy to mitigate their possible kinetic limitations in three-dimensional architectures.
Project description:Formation of thick, high energy density, flexible solid supercapacitors is challenging because of difficulties infilling gel electrolytes into porous electrodes. Incomplete infilling results in a low capacitance and poor mechanical properties. Here we report a bottom-up infilling method to overcome these challenges. Electrodes up to 500??m thick, formed from multi-walled carbon nanotubes and a composite of poly(3,4-ethylenedioxythiophene), polystyrene sulfonate and multi-walled carbon nanotubes are successfully infilled with a polyvinyl alcohol/phosphoric acid gel electrolyte. The exceptional mechanical properties of the multi-walled carbon nanotube-based electrode enable it to be rolled into a radius of curvature as small as 0.5?mm without cracking and retain 95% of its initial capacitance after 5000 bending cycles. The areal capacitance of our 500??m thick poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, multi-walled carbon nanotube-based flexible solid supercapacitor is 2662?mF?cm-2 at 2?mV?s-1, at least five times greater than current flexible supercapacitors.
Project description:Extensive efforts have recently been devoted to the construction of aqueous rechargeable sodium-ion batteries (ARSIBs) for large-scale energy-storage applications due to their desired properties of abundant sodium resources and inherently safer aqueous electrolytes. However, it is still a significant challenge to develop highly flexible ARSIBs ascribing to the lack of flexible electrode materials. In this work, nanocube-like KNiFe(CN)6 (KNHCF) and rugby ball-like NaTi2(PO4)3 (NTP) are grown on carbon nanotube fibers via simple and mild methods as the flexible binder-free cathode (KNHCF@CNTF) and anode (NTP@CNTF), respectively. Taking advantage of their high conductivity, fast charge transport paths, and large accessible surface area, the as-fabricated binder-free electrodes display admirable electrochemical performance. Inspired by the remarkable flexibility of the binder-free electrodes and the synergy of KNHCF@CNTF and NTP@CNTF, a high-performance quasi-solid-state fiber-shaped ARSIB (FARSIB) is successfully assembled for the first time. Significantly, the as-assembled FARSIB possesses a high capacity of 34.21 mAh cm-3 and impressive energy density of 39.32 mWh cm-3. More encouragingly, our FARSIB delivers superior mechanical flexibility with only 5.7% of initial capacity loss after bending at 90° for over 3000 cycles. Thus, this work opens up an avenue to design ultraflexible ARSIBs based on all binder-free electrodes for powering wearable and portable electronics.
Project description:A rechargeable lithium anode requires a porous structure for a high capacity, and a stable electrode/electrolyte interface against dendrite formation and polysulfide crossover when used in a lithium-sulfur battery. Here, we design two simple steps of spontaneous reactions for protecting porous lithium electrodes. First, a reaction between molten lithium and sulfur-impregnated carbon nanofiber forms a fibrous network with a lithium shell and a carbon core. Second, we coat the surface of this porous lithium electrode with a composite of lithium bismuth alloys and lithium fluoride through another spontaneous reaction between lithium and bismuth trifluoride, solvated with phosphorous pentasulfide, which also polymerizes with lithium sulfide residual in the electrode to form a solid electrolyte layer. This protected porous lithium electrode enables stable operation of a lithium-sulfur battery with a sulfur loading of 10.2 mg cm-2 at 6.0 mA cm-2 for 200 cycles.
Project description:Fabrication of precursor-derived ceramic fibers as electrodes for energy storage applications remains largely unexplored. Within this work, three little known polymer-derived ceramic (PDC)-based fibers are being studied systemically as potential high-capacity electrode materials for electrochemical energy devices. We report fabrication of precursor-derived SiOC fibermats via one-step spinning from various compositions of siloxane oligomers followed by stabilization and pyrolysis at 800 °C. Electron microscopy, Raman, FTIR, XPS, and NMR spectroscopies reveal transformation from polymer to ceramic stages of the various SiOC ceramic fibers. The ceramic samples are a few microns in diameter with a free carbon phase embedded in the amorphous Si-O-C structure. The free carbon phase improves the electronic conductivity and provides major sites for ion storage, whereas the Si-O-C structure contributes to high efficiency. The self-standing electrodes in lithium-ion battery half-cells deliver a charge capacity of 866 mA h gelectrode -1 with a high initial coulombic efficiency of 72%. As supercapacitor electrode, SiOC fibers maintain 100% capacitance over 5000 cycles at a current density of 3 A g-1.
Project description:It is generally accepted that solid-electrolyte interphase formed on the surface of lithium-battery electrodes play a key role in controlling their cycling performance. Although a large variety of surface-sensitive spectroscopies and microscopies were used for their characterization, the focus was on surface species nature rather than on the mechanical properties of the surface films. Here we report a highly sensitive method of gravimetric and viscoelastic probing of the formation of surface films on composite Li4Ti5O12 electrode coupled with lithium ions intercalation into this electrode. Electrochemical quartz-crystal microbalance with dissipation monitoring measurements were performed with LiTFSI, LiPF6, and LiPF6?+?2% vinylene carbonate solutions from which structural parameters of the surface films were returned by fitting to a multilayer viscoelastic model. Only a few fast cycles are required to qualify surface films on Li4Ti5O12 anode improving in the sequence LiPF6?<?LiPF6?+?2% vinylene carbonate << LiTFSI.
Project description:Aqueous supercapacitors are powerful energy sources, but they are limited by energy density that is much lower than lithium-ion batteries. Since raising the voltage beyond the thermodynamic potential for water splitting (1.23 V) can boost the energy density, there has been much effort on water-stabilizing salvation additives such as Li2SO4 that can provide an aqueous electrolyte capable of withstanding ~1.8 V. Guided by the first-principles calculations that reveal water can promote hydrogen and oxygen evolution reactions, here, we pursue a new strategy of covering the electrode with a dense electroplated polymerized polyacrylic acid, which is an electron insulator but a proton conductor and proton reservoir. The combined effect of salvation and coating expands the electrochemical window throughout pH 3 to pH 10 to 2.4 V for both fast and slow proton-mediated redox reactions. This allows activated carbon to quadruple the energy density, a kilogram of nitrogen-doped graphene to provide 127 Watt-hour, and both to have improved endurance because of suppression of water-mediated corrosion. Therefore, aqueous supercapacitors can now achieve energy densities quite comparable to that of a lithium-ion battery, but at 100 times the charging/discharging speed and cycle durability.