Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic conductivity and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.
Lithium metal (Li ) rechargeable batteries (LMBs), such as systems with a Li anode and intercalation and/or conversion type cathode, lithium-sulfur (Li-S), and lithium-oxygen (O )/air (Li-O /air) batteries, are becoming increasingly important for electrifying the modern transportation system, with the aim of sustainable mobility. Although some rechargeable LMBs (e.g. Li /LiFePO batteries from Bolloré Bluecar, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is hampered by a number of formidable challenges, including growth of lithium dendrites, electrolyte instability towards high voltage intercalation-type cathodes, the poor electronic and ionic conductivities of sulfur (S ) and O , as well as their corresponding reduction products (e.g. Li S and Li O), dissolution, and shuttling of polysulfide (PS) intermediates. This leads to a short lifecycle, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. The use of electrolyte additives is considered one of the most economical and effective approaches for circumventing these problems. This Review gives an overview of the various functional additives that are being applied and aims to stimulate new avenues for the practical realization of these appealing devices.
A novel single lithium-ion (Li-ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI(-)), and high-molecular-weight poly(ethylene oxide) (PEO). The neat LiPSsTFSI ionomer displays a low glass-transition temperature (44.3 °C; that is, strongly plasticizing effect). The complex of LiPSsTFSI/PEO exhibits a high Li-ion transference number (tLi (+) =0.91) and is thermally stable up to 300 °C. Meanwhile, it exhibits a Li-ion conductivity as high as 1.35×10(-4) S cm(-1) at 90 °C, which is comparable to that for the classic ambipolar LiTFSI/PEO SPEs at the same temperature. These outstanding properties of the LiPSsTFSI/PEO blended polymer electrolyte would make it promising as solid polymer electrolytes for Li batteries.
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 salts in SPEs and the polysulfide species formed during the cycling. The corresponding Li-S cells deliver high specific/areal capacity (1394 mAh g, 1.2 mAh cm), good Coulombic efficiency, and superior rate capability (∼800 mAh g after 60 cycles). These results imply the importance of the molecular structure of lithium salts in ASSLSBs and pave a way for future development of safe and cost-effective Li-S batteries.
Solid polymer electrolytes (SPEs) comprising lithium bis(fluorosulfonyl)imide (Li[N(SOF)], LiFSI) and poly(ethylene oxide) (PEO) have been studied as electrolyte material and binder for the Li-S polymer cell. The LiFSI-based Li-S all solid polymer cell can deliver high specific discharge capacity of 800 mAh g (i.e., 320 mAh g), high areal capacity of 0.5 mAh cm, and relatively good rate capability. The cycling performances of Li-S polymer cell with LiFSI are significantly improved compared with those with conventional LiTFSI (Li[N(SOCF)]) salt in the polymer membrane due to the improved stability of the Li anode/electrolyte interphases formed in the LiFSI-based SPEs. These results suggest that the LiFSI-based SPEs are attractive electrolyte materials for solid-state Li-S batteries.
Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO ).
All-solid-state lithium-sulfur batteries (ASSLSBs) offer a means to enhance the energy density and safety of the state-of-art lithiumion batteries (LIBs), due to their high gravimetric energy density, low cost and environmental benignancy. In this work, the status of the research advances and perspectives on several types of solid electrolytes (SEs) developed for ASSLSBs are reviewed. The promises and challenges of utilizing SEs are discussed taking into account both theoretical calculation and experimental results, in hope of shedding some lights on future design of high energy density, cost competitive, and safe Li-S batteries. Lithium-sulfur (Li-S) batteries have been extensively investigated for lightweight applications (e.g., aircraft, artificial satellite, and unmanned aerial vehicles), and large-scale stationary energy storage, owing to their high gravimetric energy density, low cost, and environmental friendliness.1-3 The deployment of Li-S batteries into commercial market is hampered by several seemingly intrinsic problems resulting from the complex cell chemistry. Firstly, the electronically insulating nature of elemental sulfur (S 8 ) and end-product lithium sulfide (Li 2 S) leads to unstable electrochemical contact within S cathode. [4][5][6][7] Secondly, the soluble intermediates of polysulfide (PS) can diffuse between the cathode and anode (i.e., shuttle effect of PS), generating an active material loss in S cathode and degrading metallic Li anode. [4][5][6][7][8][9] Thirdly, the formation of 'dead' Li and Li dendrites upon cycling could not only decrease the Coulombic efficiency but also raise safety issues. [10][11][12] In recent years, various strategies have been attempted to overcome the above-mentioned problems. Most of the efforts have been devoted to enhance the electrochemical performance of Li-S batteries using well-designed cathode materials. 13 The diffusion of polysulfide species generated during discharge into electrolytes can be significantly suppressed by infusing sulfur into carbon materials in the cathode with an adequately controlled and engineered porosity and pore size, thus increasing the practical capacity and cyclability of Li-S batteries. These rational and creative strategies of cathode design have been covered by a number of recent reviews. 7,14,15 Besides, new binders (e.g., poly(ethylene oxide) (PEO) 16 and carboxymethycellulose (CMC) 17,18 ) have been employed for guarantying the integrity of the morphology and structure of S cathode, and enhancing the adhesion to current collector. The modification of separators (e.g., multiwall carbon nanotubes coated polypropylene 19 and lithiated Nafion 20 ) have been also developed for reducing the migration of polysulfides, thus mitigating the shuttle effect of PS. 21Apart from the strategies mentioned above, another approach, focusing on electrolyte formulation and modification, has been proved to be effective. The performances of Li-S batteries are largely affected by the electrolyte recipes, such as the type and identity of so...
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