Project description:Solid-state electrolytes (SSEs) are receiving great interest because their high mechanical strength and transference number could potentially suppress Li dendrites and their high electrochemical stability allows the use of high-voltage cathodes, which enhances the energy density and safety of batteries. However, the much lower critical current density and easier Li dendrite propagation in SSEs than in nonaqueous liquid electrolytes hindered their possible applications. Herein, we successfully suppressed Li dendrite growth in SSEs by in situ forming an LiF-rich solid electrolyte interphase (SEI) between the SSEs and the Li metal. The LiF-rich SEI successfully suppresses the penetration of Li dendrites into SSEs, while the low electronic conductivity and the intrinsic electrochemical stability of LiF block side reactions between the SSEs and Li. The LiF-rich SEI enhances the room temperature critical current density of Li3PS4 to a record-high value of >2 mA cm-2. Moreover, the Li plating/stripping Coulombic efficiency was escalated from 88% of pristine Li3PS4 to more than 98% for LiF-coated Li3PS4. In situ formation of electronic insulating LiF-rich SEI provides an effective way to prevent Li dendrites in the SSEs, constituting a substantial leap toward the practical applications of next-generation high-energy solid-state Li metal batteries.
Project description:Solid-state Li-O2 batteries (SSLOBs) have attracted considerable attention because of their high energy density and superior safety. However, their sluggish kinetics have severely impeded their practical application. Despite efforts to design highly efficient catalysts, efficient oxygen reaction evolution at gas-solid interfaces and fast transport pathways in solid-state electrodes remain challenging. Here, we develop a dual electronic-ionic microenvironment to substantially enhance oxygen electrolysis in solid-state batteries. By designing a lithium-decorative catalyst with an engineering crystal structure, the coordinatively unsaturated sites and high concentration of defects alleviate the limitations of electronic-ionic transport in solid interfaces and create a balanced gas-solid microenvironment for solid-state oxygen electrolysis. This strategy facilitates oxygen reduction reaction, mediates the transport of reaction species, and promotes the decomposition of the discharge products, contributing to a high specific capacity with a stable cycling life. Our work provides previously unknown insight into structure-property relationships in solid-state electrolysis for SSLOBs.
Project description:Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO2-embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO2-based anode and a LiNi1/3Co1/3Mn1/3O2-based cathode shows a good performance of 2040?Wh/kg at 268.6?W/kg based on the anode material weight.
Project description:To match the high capacity of metallic anodes, all-solid-state batteries require high energy density, long-lasting composite cathodes such as Ni-Mn-Co (NMC)-based lithium oxides mixed with a solid-state electrolyte (SSE). However in practice, cathode capacity typically fades due to NMC cracking and increasing NMC/SSE interface debonding because of NMC pulverization, which is only partially mitigated by the application of a high cell pressure during cycling. Using smart processing protocols, we report a single-crystal particulate LiNi0.83Mn0.06Co0.11O2 and Li6PS5Cl SSE composite cathode with outstanding discharge capacity of 210 mA h g-1 at 30 °C. A first cycle coulombic efficiency of >85, and >99% thereafter, was achieved despite a 5.5% volume change during cycling. A near-practical discharge capacity at a high areal capacity of 8.7 mA h cm-2 was obtained using an asymmetric anode/cathode cycling pressure of only 2.5 MPa/0.2 MPa.
Project description:The growing demand of flexible electronic devices is increasing the requirements of their power sources. The effect of bending in thin-film batteries is still not well understood. Here, we successfully developed a high active area flexible all-solid-state battery as a model system that consists of thin-film layers of Li4Ti5O12, LiPON, and Lithium deposited on a novel flexible ceramic substrate. A systematic study on the bending state and performance of the battery is presented. The battery withstands bending radii of at least 14 mm achieving 70% of the theoretical capacity. Here, we reveal that convex bending has a positive effect on battery capacity showing an average increase of 5.5%, whereas concave bending decreases the capacity by 4% in contrast with recent studies. We show that the change in capacity upon bending may well be associated to the Li-ion diffusion kinetic change through the electrode when different external forces are applied. Finally, an encapsulation scheme is presented allowing sufficient bending of the device and operation for at least 500 cycles in air. The results are meant to improve the understanding of the phenomena present in thin-film batteries while undergoing bending rather than showing improvements in battery performance and lifetime.
Project description:Lithium-iodine (Li-I) batteries have attracted tremendous attention due to their high energy and power densities as well as the low cost of iodine. However, the severe shuttle effect of iodine species and the uncontrollable lithium dendrite growth have strongly hindered their practical applications. Here we successfully develop a quasi-solid-state Li-I battery enabled by a MXene-based iodine cathode and a composite polymer electrolyte (CPE) containing NaNO3 particles dispersing in a pentaerythritol-tetraacrylate-based (PETEA-based) gel polymer electrolyte. As verified by experimental characterizations and first-principle calculations, the abundant functional groups on the surface of MXene sheets provide strong chemical binding to iodine species, and therefore immobilize their shuttling. The PETEA-based polymer matrix simultaneously suppresses the diffusion of iodine species and stabilizes the Li anode/CPE interface against dendrite growth. The NaNO3 particles act as an effective catalyst to facilitate the transformation kinetics of LiI3 on the cathode. Owing to such synergistic optimization, the as-developed Li-I batteries deliver high energy/power density with long cycling stability and good flexibility. This work opens up a new avenue to improve the performance of Li-I batteries.
Project description:Rational structure design is a successful approach to develop high-performance composite solid electrolytes (CSEs) for solid-state Li metal batteries. Herein, a novel CSE membrane is proposed, that consists of interwoven garnet/polyethylene oxide-Li bis(trifluoromethylsulphonyl)imide (LLZO/PEO-LiTFSI) microfibers. This CSE exhibits high Li-ion conductivity and exceptional Li dendrite suppression capability, which can be attributed to the uniform LLZO dispersion in PEO-LiTFSI and the vertical/horizontal anisotropic Li-ion conduction in the CSE. The uniform LLZO particles can generate large interaction regions between LLZO and PEO-LiTFSI, which thus form continuous Li-ion transfer pathways, retard the interfacial side reactions and strengthen the deformation resistance. More importantly, the anisotropic Li-ion conduction, that is, Li-ion transfers much faster along the microfibers than across the microfibers, can effectively homogenize the electric field distribution in the CSE during cycling, which thus prevents the excessive concentration of Li-ion flux. Finally, solid-state Li||LiFePO4 cells based on this CSE show excellent electrochemical performances. This work enriches the structure design strategy of high-performance CSEs and may be helpful for further pushing the solid-state Li metal batteries towards practical applications.
Project description:The ionic conductivity of Li6Y(BO3)3 (LYBO) was enhanced by the substitution of tetravalent ions (Zr4+ and Ce4+) for Y3+ sites through the formation of vacancies at the Li sites, an increase in compact densification, and an increase in the Li+-ion conduction pathways in the LYBO phase. As a result, the ionic conductivity of Li5.875Y0.875Zr0.1Ce0.025(BO3)3 (ZC-LYBO) reached 1.7 × 10-5 S cm-1 at 27 °C, which was about 5 orders of magnitude higher than that of undoped Li6Y(BO3)3. ZC-LYBO possessed a large electrochemical window and was thermally stable after cosintering with a LiNi1/3Mn1/3Co1/3O2 (NMC) positive electrode. These characteristics facilitated good reversible capacities in all-solid-state batteries for both NMC positive electrodes and graphite negative electrodes via a simple cosintering process.
Project description:Rechargeable Li-I2 battery has attracted considerable attentions due to its high theoretical capacity, low cost and environment-friendliness. Dissolution of polyiodides are required to facilitate the electrochemical redox reaction of the I2 cathode, which would lead to a harmful shuttle effect. All-solid-state Li-I2 battery totally avoids the polyiodides shuttle in a liquid system. However, the insoluble discharge product at the conventional solid interface results in a sluggish electrochemical reaction and poor rechargeability. In this work, by adopting a well-designed hybrid electrolyte composed of a dispersion layer and a blocking layer, we successfully promote a new polyiodides chemistry and localize the polyiodides dissolution within a limited space near the cathode. Owing to this confined dissolution strategy, a rechargeable and highly reversible all-solid-state Li-I2 battery is demonstrated and shows a long-term life of over 9000 cycles at 1C with a capacity retention of 84.1%.
Project description:Li4Ti5O12 (LTO) and hard carbon (HC) are commonly used anodes in the Li-ion batteries. LTO has an operating voltage of 1.55 V and exhibits high-rate performance but with limited capacity. HC has high specific capacity but extremely low operating voltage. Herein, we show that a simple physical mixture of the two enhances the half-cell as well as full-cell performance through a synergistic cooperation between the materials. Specifically, the LTO-HC mixed anodes exhibit impressive performance even at high C-rates. This results from a quick internalization of Li ions by LTO followed by their distribution to HC regions via the high density of the winding internal interfaces between the two. The full cells of the LTO-HC mixed anodes with LiCoO2 (LCO) evince an enhanced operating voltage window and a well-defined plateau. Because of a reduced irreversible capacity loss in the LCO/mixed anode full cells, the overall specific capacity is better than the LCO/pristine anode full cells. Also, with the LTO-HC 20-80 anode (Li content reduced by 80%), the full cell exhibits an impressive performance when compared to pristine anodes without pre-lithiation. The LCO/mixed anode full cells have excellent cycling stability up to 500 cycles at a current density of 100 mA g-1.