Project description:The dendrite growth of Li anodes severely degrades the performance of lithium-oxygen (Li-O2) batteries. Recently, hybrid solid electrolyte (HSE) has been regarded as one of the most promising routes to tackle this problem. However, before this is realized, the HSE needs to simultaneously satisfy contradictory requirements of high modulus and even, flexible contact with Li anode, while ensuring uniform Li+ distribution. To tackle this complex dilemma, here, an HSE with rigid Li1.5Al0.5Ge1.5(PO4)3 (LAGP) core@ultrathin flexible poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) shell interface has been developed. The introduced large amount of nanometer-sized LAGP cores can not only act as structural enhancer to achieve high Young's modulus but can also construct Li+ diffusion network to homogenize Li+ distribution. The ultrathin flexible PVDF-HFP shell provides soft and stable contact between the rigid core and Li metal without affecting the Li+ distribution, meanwhile suppressing the reduction of LAGP induced by direct contact with Li metal. Thanks to these advantages, this ingenious HSE with ultra-high Young's modulus of 25 GPa endows dendrite-free Li deposition even at a deposition capacity of 23.6 mAh. Moreover, with the successful inhibition of Li dendrites, the HSE-based quasi-solid-state Li-O2 battery delivers a long cycling stability of 146 cycles, which is more than three times that of gel polymer electrolyte-based Li-O2 battery. This new insight may serve as a starting point for further designing of HSE in Li-O2 batteries, and can also be extended to various battery systems such as sodium-oxygen batteries.
Project description:Herein, we employed Bi and Sb as the negative electrode in all solid-state lithium-ion batteries (LIBs) using LiBH4 as the solid-state electrolyte. The composite anode materials with acetylene black (AB) and LiBH4, prepared by high energy ball-milling, have shown extremely high stability with a high coulombic efficiency of 90-99% over a number of cycles. The gravimetric capacity decayed by only 18 and 5% as compared to the initial volumetric capacity of 4681.7 and 4393.4 mA h cm-3 for Bi and Sb anodes respectively.
Project description:The notorious lithium dendrite growth, causing the safety concern, hinders the practical application of high-capacity Li metal anodes for rechargeable batteries. Here, a robust and highly ionic conductive solid electrolyte interphase (SEI) layer to protect Li metal anode is in-situ constructed by introducing trace additive of tetrapotassium heptaiodobismuthate (K4BiI7) into electrolyte. The K4BiI7-added electrolyte enables Li metal anode to display a stable cycling for over 600 cycles at 1.0 mA cm-2/1.0 mAh cm-2 and over 400 cycles at 5.0 mA cm-2/5.0 mAh cm-2. In situ optical microscopy observations also conform the suppression of Li dendrites at high current density. Moreover, the in-situ SEI layer modified Li anode exhibits an average Coulombic efficiency of 99.57% and less Li dendrite growth. The Li-S full sells with the modified electrolyte also show improved electrochemical performance. This research provides a cost-efficient method to achieve a highly ionic conductive and stable SEI layer toward advanced Li metal anodes.
Project description:Most highly Li-conducting solid electrolytes (σRT > 10-3 S cm-1) are unstable against lithium-metal and suffer from detrimental solid-electrolyte decomposition at the lithium-metal/solid-electrolyte interface. Solid electrolytes that are stable against lithium metal thus offer a direct route to stabilize lithium-metal/solid-electrolyte interfaces, which is crucial for realizing all-solid-state batteries that outperform conventional lithium-ion batteries. In this study, we investigate Li5NCl2 (LNCl), a fully-reduced solid electrolyte that is thermodynamically stable against lithium metal. Combining experiments and simulations, we investigate the lithium diffusion mechanism, different synthetic routes, and the electrochemical stability window of LNCl. Li nuclear magnetic resonance (NMR) experiments suggest fast Li motion in LNCl, which is however locally confined and not accessible in macroscopic LNCl pellets via electrochemical impedance spectroscopy (EIS). With ab-initio calculations, we develop an in-depth understanding of Li diffusion in LNCl, which features a disorder-induced variety of different lithium jumps. We identify diffusion-limiting jumps providing an explanation for the high local diffusivity from NMR and the lower macroscopic conductivity from EIS. The fundamental understanding of the diffusion mechanism we develop herein will guide future conductivity optimizations for LNCl and may be applied to other highly-disordered fully-reduced electrolytes. We further show experimentally that the previously reported anodic limit (>2 V vs Li+/Li) is an overestimate and find the true anodic limit at 0.6 V, which is in close agreement with our first-principles calculations. Because of LNCl's stability against lithium-metal, we identify LNCl as a prospective artificial protection layer between highly-conducting solid electrolytes and strongly-reducing lithium-metal anodes and thus provide a computational investigation of the chemical compatibility of LNCl with common highly-conducting solid electrolytes (Li6PS5Cl, Li3YCl6, ...). Our results set a framework to better understand and improve highly-disordered fully-reduced electrolytes and highlight their potential in enabling lithium-metal solid-state batteries.
Project description:The performance of nanocomposite electrodes prepared by controlled ball-milling of TiS? and a Li?S-P?S? solid electrolyte (SE) for all-solid-state lithium batteries is investigated, focusing on the evolution of the microstructure. Compared to the manually mixed electrodes, the ball-milled electrodes exhibit abnormally increased first-charge capacities of 416 mA h g(-1) and 837 mA h g(-1) in the voltage ranges 1.5-3.0 V and 1.0-3.0 V, respectively, at 50 mA g(-1) and 30°C. The ball-milled electrodes also show excellent capacity retention of 95% in the 1.5-3.0 V range after 60 cycles as compared to the manually mixed electrodes. More importantly, a variety of characterization techniques show that the origin of the extra Li(+) storage is associated with an amorphous Li-Ti-P-S phase formed during the controlled ball-milling process.
Project description:Since the launch of lithium-ion batteries, elements (such as silicon, tin, or aluminum) that can be alloyed with lithium have been expected as anode materials, owing to larger capacity. However, their successful application has not been accomplished because of drastic structural degradation caused by cyclic large volume change during battery reactions. To prolong lifetime of alloy anodes, we must circumvent the huge volume strain accompanied by insertion/extraction of lithium. Here we report that by using aluminum-foil anodes, the volume expansion during lithiation can be confined to the normal direction to the foil and, consequently, the electrode cyclability can be markedly enhanced. Such a unidirectional volume-strain circumvention requires an appropriate hardness of the matrix and a certain tolerance to off-stoichiometry of the resulting intermetallic compound, which drive interdiffusion of matrix component and lithium along the normal-plane direction. This metallurgical concept would invoke a paradigm shift to future alloy-anode battery technologies.
Project description:All-solid-state batteries based on non-combustible solid electrolytes are promising candidates for safe energy storage systems. In addition, they offer the opportunity to utilize metallic lithium as an anode. However, it has proven to be a challenge to design an electrolyte that combines high ionic conductivity and processability with thermodynamic stability toward lithium. Herein, we report a new highly conducting solid solution that offers a route to overcome these challenges. The Li-P-S ternary was first explored via a combination of high-throughput crystal structure predictions and solid-state synthesis (via ball milling) of the most promising compositions, specifically, phases within the Li3P-Li2S tie line. We systematically characterized the structural properties and Li-ion mobility of the resulting materials by X-ray and neutron diffraction, solid-state nuclear magnetic resonance spectroscopy (relaxometry), and electrochemical impedance spectroscopy. A Li3P-Li2S metastable solid solution was identified, with the phases adopting the fluorite (Li2S) structure with P substituting for S and the extra Li+ ions occupying the octahedral voids and contributing to the ionic transport. The analysis of the experimental data is supported by extensive quantum-chemical calculations of both structural stability, diffusivity, and activation barriers for Li+ transport. The new solid electrolytes show Li-ion conductivities in the range of established materials, while their composition guarantees thermodynamic stability toward lithium metal anodes.
Project description:Poly(ethylene oxide) (PEO) electrolytes usually suffer from low room temperature (RT) ionic conductivity and a narrow voltage window, which limits the improvement of energy density and practical applications in all-solid-state batteries. Composite polymer electrolytes (CPEs) are regarded as the common method to reduce the crystallinity of polymers and increase the lithium ion conductivity. Compared with active or inert ceramic material fillers in previous studies, aluminum-lithium alloy fillers are used to prepare composite electrolytes in this study, showing excellent performance at room temperature. The conductivity of the PEO-based electrolytes increases by a factor of 3.62-3.62× 10-4 S cm-1 at RT with 5 wt % Al-Li alloy. The transference number of Li+ is increased to 0.524. The characteristics of the Al-Li alloy and higher conductivity enable the composite electrolyte to stabilize the interface with the electrodes, reducing the polarization of solid-state batteries. The all-solid-state Li/PEO-5%/LiFePO4 cells show the highest initial discharge capacity of 153 mAh g-1 and the highest stable discharge capacity of 147 mAh g-1 with the initial Coulombic efficiency of more than 100%. It also exhibits the best rate capacity and cycle performance (90% capacity retention rate after 100 cycles).
Project description:Many phase transformations associated with solid-state precipitation look structurally simple, yet, inexplicably, take place with great difficulty. A classic case of difficult phase transformations is the nucleation of strengthening precipitates in high-strength lightweight aluminium alloys. Here, using a combination of atomic-scale imaging, simulations and classical nucleation theory calculations, we investigate the nucleation of the strengthening phase θ' onto a template structure in the aluminium-copper alloy system. We show that this transformation can be promoted in samples exhibiting at least one nanoscale dimension, with extremely high nucleation rates for the strengthening phase as well as for an unexpected phase. This template-directed solid-state nucleation pathway is enabled by the large influx of surface vacancies that results from heating a nanoscale solid. Template-directed nucleation is replicated in a bulk alloy as well as under electron irradiation, implying that this difficult transformation can be facilitated under the general condition of sustained excess vacancy concentrations.
Project description:Lithium-ion batteries (LIBs) are generally constructed by lithium-including positive electrode materials, such as LiCoO2, and lithium-free negative electrode materials, such as graphite. Recently, lithium-free positive electrode materials, such as sulfur, are gathering great attention from their very high capacities, thereby significantly increasing the energy density of LIBs. Though the lithium-free materials need to be combined with lithium-containing negative electrode materials, the latter has not been well developed yet. In this work, the feasibility of Li-rich Li-Si alloy is examined as a lithium-containing negative electrode material. Li-rich Li-Si alloy is prepared by the melt-solidification of Li and Si metals with the composition of Li21Si5. By repeating delithiation/lithiation cycles, Li-Si particles turn into porous structure, whereas the original particle size remains unchanged. Since Li-Si is free from severe constriction/expansion upon delithiation/lithiation, it shows much better cyclability than Si. The feasibility of the Li-Si alloy is further examined by constructing a full-cell together with a lithium-free positive electrode. Though Li-Si alloy is too active to be mixed with binder polymers, the coating with carbon-black powder by physical mixing is found to prevent the undesirable reactions of Li-Si alloy with binder polymers, and thus enables the construction of a more practical electrochemical cell.