Understanding the Role of Nano-Aluminum Oxide in All-Solid-State Lithium-Sulfur Batteries (original) (raw)
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High performance all-solid-state lithium/sulfur batteries using lithium argyrodite electrolyte
Journal of Solid State Electrochemistry, 2014
suffer from safety problems arising from lithium anode and fast capacity fading due to the insulating nature of sulfur, the dissolution-induced polysulfide shuttle reaction, and large volume changes. [4-6] To address these issues, carbonaceous material [7,8] and conducting polymers [9] have been used to trap the high-order polysulfides in the cathodes; protective layers and electrolyte additives are employed for protection of metallic-lithium anodes from reactions with polysulfide. [10,11] However, the shuttle reaction still exists, and the safety issue induced by lithium dendrite is still a great challenge. All-solid-state Li-S batteries can completely inhibit the dissolution of polysulfide, eliminate the polysulfide shuttle, and avoid lithium dendrite formation. [12-19] However, the use of rigid solid electrolytes in all-solid-state Li-S batteries also increases the stress/strain and interface resistance and reduce the reaction kinetics. [20-22] The key challenge is to minimize stress/strain and to construct a robust electronic and ionic pathway in the sulfur cathode, due to the electronic/ionic insulting nature of sulfur. For enhancing the electronic conductivity and reducing the electronic contact resistance, Kobayashi et al. synthesized a sulfur and acetylene black (AB) nanocomposite cathode using a gas-phase mixing method, and reported a reversible capacity of 900 mA h g −1 at a current density of 0.013 mA cm −2 in all-solid-state batteries. [23] The sulfur and carbon-nanofibers composite cathode also shows a high capacity in the all-solid-state Li-S batteries. [24] To ensure high ionic conduction in the sulfur cathode, Lin et al. synthesized core-shell structured lithium-sulfide nanoparticles with an Li 3 PS 4 electrolyte as shell, showing six orders of magnitude higher in ionic conductivity than that of bulk lithiumsulfide. Excellent cyclic performance was demonstrated for allsolid-state Li-S batteries at 60 °C. [13] By incorporation of five sulfur atoms in the Li 3 PS 4 electrolyte, the Li 3 PS 4+5 cathode with loading density of 0.25-0.6 mg cm −2 exhibits excellent cycling stability for all-solid-state Li-S batteries. [14] These studies demonstrate that a close contact of the nanosulfur, either to carbon or to electrolytes, and uniformly distributing these composites into an ionic/electronic conducting matrix, can significantly improve the electrochemical performances of solid-state Li-S cell because the nano-sulfur contacts both the highly ionic and Safety and the polysulfide shuttle reaction are two major challenges for liquid electrolyte lithium-sulfur (Li-S) batteries. Although use of solid-state electrolytes can overcome these two challenges, it also brings new challenges by increasing the interface resistance and stress/strain. In this work, the interface resistance and stress/strain of sulfur cathodes are significantly reduced by conformal coating ≈2 nm sulfur (S) onto reduced graphene oxide (rGO). An Li-S full cell consisting of an rGO@S-Li 10 GeP 2 S 12-acetylene black (AB) composite cathode is evaluated. At 60 °C, the all-solid-state Li-S cell demonstrates a similar electrochemical performance as in liquid organic electrolyte, with high rate capacities of 1525.
The search for a solid electrolyte, as a polysulfide barrier, for lithium/sulfur batteries
Journal of Solid State Electrochemistry, 2016
Composite Li 10 SnP 2 S 12 (LSPS)/polyethylene oxide (PEO) films, containing 25 to 50 % polymer, were electrophoretically deposited from acetone-based suspension and tested as possible candidates for polysulfide barriers in Li/S batteries. It was found by XRD and XPS tests that saturation of composite films by LiI salt, followed by prolonged annealing at 90°C, diminishes the crystallinity of neat LSPS and results in the formation of a novel composite Li 10+x I x SnP 2 S 12 (LISPS)/P(EO) 3 /LiI solid electrolyte (x < 1). The high roomtemperature ion conductivity of amorphous sulfide Li 10+ x I x SnP 2 S 12 (0.1-0.3 mS cm −1) is restricted by slow ion transport via the polymer electrolyte (PE) imbedded in ceramics and grain boundaries between the PE and sulfide. Increase in polymer content and temperature improves total ion transport in the LISPS/PEO system. Conformal EPD coating of sulfur and lithium sulfide cathodes by the developed composite electrolyte increased the reversible capacity and Faradaic efficiency of the Li/S and Li/Li 2 S cells and enabled their operation at 60°C.
Nanoscale stabilization of Li–sulfur batteries by atomic layer deposited Al2O3
RSC Advances, 2014
An atomic layer deposited (ALD) Al 2 O 3 coating applied to sulfur cathodes has been studied in this paper. It is demonstrated that the Al 2 O 3 coating improves the cycling stability of Li-sulfur batteries. The underlying mechanism by synchrotron-based X-ray photoelectron spectroscopy was investigated. The coating layer not only protects the polysulfide from dissolution, but also facilitates the utilization of sulfur, demonstrating improved electrochemical performances.
High Capacity All-Solid-State Lithium Batteries Enabled by Pyrite-Sulfur Composites
Advanced Energy Materials, 2018
electric vehicles. [1,2,4] For this purpose, novel chemistries involving conversion reactions [2,3] are widely studied as they promise substantially improved specific energy densities. [5] Among several candidates, those involving the sulfur conversion reaction at the positive electrode are one of the most promising for nextgeneration batteries. [6] The conversion reaction of sulfur with lithium (S + 2Li ⇄ Li 2 S) can theoretically deliver a specific capacity of 1672 mAh g −1 at an average discharge voltage of 2.15 V, translating in a gravimetric energy density up to 2510 Wh kg −1. [6,7] This value is three times higher than that of cathodes employed in the current generation of lithium-ion batteries. [2] Furthermore, sulfur is the 15th most abundant element on earth's crust. Being also nontoxic and environmentally benign, it is of a rather low-cost when compared with the present nickel and cobalt-based transition metal oxide cathodes. [8-10] Unfortunately though, the commercialization of Li-S batteries is still hindered by a few issues effectively limiting both the practical energy density and the cycle life. [7] Most of these challenges relate to the reaction mechanism leading to the full conversion of sulfur to lithium disulfide, which is associated with the formation of intermediate high-and low-order polysulfides. Such polysulfides are highly soluble in conventional liquid electrolytes. This results in high self-discharge rates, due to the shuttling of polysulfides between the electrodes, and electrodes degradation, due to both the dissolution of active material (cathode) and the reactivity of the above-mentioned intermediates with metallic lithium (anode). [7] The situation is aggravated by a relatively large volumetric expansion/contraction (of about 80%) upon cycling, [7] which facilitates polysulfide dissolution and causes major structural and morphological changes leading to loss of contact and fast performance degradation. Finally, sulfur, lithium disulfide, and all reaction intermediates are characterized by a very low e − conductivity. [7] In the past years, several strategies have been developed to address the above-mentioned issues. Some involve the use of composite positive electrode materials, for example, sulfurcarbon [11] (with particular attention at functionalized carbons [12]), sulfur-transition metal oxides, [13] sulfur metal sulfides, [14] sulfurgraphene, [15] sulfur-polymer, [16] among others. Composites As the theoretical limit of intercalation material-based lithium-ion batteries is approached, alternative chemistries based on conversion reactions are presently considered. The conversion of sulfur is particularly appealing as it is associated with a theoretical gravimetric energy density up to 2510 Wh kg −1. In this paper, three different carbon-iron disulfide-sulfur (C-FeS 2-S) composites are proposed as alternative positive electrode materials for all-solid-state lithiumsulfur batteries. These are synthesized through a facile, low-cost, single-step ball-milling procedure. It is found that the crystalline structure (evaluated by X-ray diffraction) and the morphology of the composites (evaluated by scanning electron microscopy) are greatly influenced by the FeS 2 :S ratio. Li/LiI-Li 3 PS 4 /C-FeS 2-S solid-state cells are tested under galvanostatic conditions, while differential capacity plots are used to discuss the peculiar electrochemical features of these novel materials. These cells deliver capacities as high as 1200 mAh g (FeS 2 +S) −1 at the intermediate loading of 1 mg cm −2 (1.2 mAh cm −2), and up to 3.55 mAh cm −2 for active material loadings as high as 5 mg cm −2 at 20 °C. Such an excellent performance, rarely reported for (sulfur/metal sulfide)based, all solid-state cells, makes these composites highly promising for real application where high positive electrode loadings are required.
2024
Sulfide solid electrolytes are regarded as a pivotal component for all-solid-state lithium batteries (ASSLBs) due to their inherent advantages, such as high ionic conductivity and favorable mechanical properties. However, persistent challenges related to electrochemical stability and interfacial compatibility have remained significant hurdles in their practical application. To address these issues, we propose an anion-cation co-doping strategy for the optimization of Li7P3S11 (LPS) through chemical bonding and structural modifications. The co‐doping effects on the structural and electrochemical properties of SiO2-, GeO2-, and SnO2-doped sulfide electrolytes were systematically investigated. Cations are found to preferentially substitute the P5+ of the P2S74- unit within the LPS matrix, thereby expanding the Li+ diffusion pathways and introducing lithium defects to facilitate ion conduction. Concurrently, oxygen ions partially substitute sulfur ions, leading to improved electrochemical stability and enhanced interfacial performance of the sulfide electrolyte. The synergistic effects resulting from the incorporation of oxides yield several advantages, including superior ionic conductivity, enhanced interfacial stability, and effective suppression of lithium dendrite formation. Consequently, the application of oxide-doped sulfide solid electrolytes in ASSLBs yields promising electrochemical performances. The cells with doped-electrolytes exhibit higher initial coulombic efficiency, superior rate capability, and cycling stability when compared to the pristine LPS. Overall, this research highlights the potential of oxide-doped sulfide solid electrolytes in the development of advanced ASSLBs.
Aluminum and lithium sulfur batteries: a review of recent progress and future directions
Journal of Physics: Condensed Matter, 2021
Advanced materials with various micro-/nanostructures have attracted plenty of attention for decades in energy storage devices such as rechargeable batteries (ion- or sulfur based batteries) and supercapacitors. To improve the electrochemical performance of batteries, it is uttermost important to develop advanced electrode materials. Moreover, the cathode material is also important that it restricts the efficiency and practical application of aluminum-ion batteries. Among the potential cathode materials, sulfur has become an important candidate material for aluminum-ion batteries cause of its considerable specific capacity. Two-dimensional materials are currently potential candidates as electrodes from lab-scale experiments to possible pragmatic theoretical studies. In this review, the fundamental principles, historical progress, latest developments, and major problems in Li–S and Al–S batteries are reviewed. Finally, future directions in terms of the experimental and theoretical ap...
Journal of the American Chemical Society, 2018
With a remarkably higher theoretical energy density compared to lithium-ion batteries (LIBs) and abundance of elemental sulfur, lithium sulfur (Li-S) batteries have emerged as one of the most promising alternatives among all the post LIB technologies. In particular, the coupling of solid polymer electrolytes (SPEs) with the cell chemistry of Li-S batteries enables a safe and high-capacity electrochemical energy storage system, due to the better processability and less flammability of SPEs compared to liquid electrolytes. However, the practical deployment of all solid-state Li-S batteries (ASSLSBs) containing SPEs is largely hindered by the low accessibility of active materials and side reactions of soluble polysulfide species, resulting in a poor specific capacity and cyclability. In the present work, an ultrahigh performance of ASSLSBs is obtained via an anomalous synergistic effect between (fluorosulfonyl)(trifluoromethanesulfonyl)imide anions inherited from the design of lithium ...
Solid State Ionics, 2018
Lithium sulphur technology for energy storage is considered to be one of the most promising of emerging technologies due to its high theoretical capacity, but the performance of these batteries is limited by problems such as dissolution of polysulphide species in electrolyte, lithium dendrite formation. Previously we demonstrated the capability of Li 6 PS 5 Cl, Li 6 PS 6 Br and Li 10 GeP 2 S 12 anode-protecting solid electrolyte membranes to mitigate these problems. To further enhance the stability of these solid electrolyte membranes, here we demonstrate that atomic layer deposition of a thin conformal coating of lithium tantalate leads to lithium polysulphide semi-flow batteries with superior performance.
Recent progress of sulfide electrolytes for all-solidstate lithium batteries
Energy Materials, 2022
Solid electrolytes are recognized as being pivotal to next-generation energy storage technologies. Sulfide electrolytes with high ionic conductivity represent some of the most promising materials to realize high-energydensity all-solid-state lithium batteries. Due to their soft nature, sulfides possess good wettability against Li metal and their preparation process is relatively effortless. High cell-level sulfide-based all-solid-state lithium batteries have gradually been realized in recent years. However, there are still several disadvantages that sulfide electrolytes need to overcome, including their sensitivity to humid air and instability to electrodes. Herein, the recent progress for sulfide electrolytes, with particular attention given to electrolyte synthesis mechanisms, electrochemical and chemical stability, interphase stabilization and all-solid-state lithium batteries with high cell-level energy density, is presented.