All‐organic batteries are a promising sustainable energy storage technology owing to the wide availability, flexibility, and recyclability of organic/polymeric compounds. The development of ...all‐organic or polymer batteries is still a challenge, as both electrode materials need to be carefully optimized to have a wide difference of redox potential and compatibility with the electrolyte. Herein, dual redox‐active polyimides based on phenothiazine and naphthalene tetracarboxylic dianhydride units are presented. After only one optimization step, the electrodes based on these dual redox polymers can be applied simultaneously as anode and cathode in a symmetric all‐organic battery. The phenothiazine functional polyimide shows two redox active voltages at around 2.5 and 3.7 V (vs. Li/Li+) with high discharge capacities of 160 mAh g−1. Moreover, the symmetric full battery delivers high power density up to 1542 W kg−1 with stable cyclability for 1000 cycles. This work demonstrates an efficient strategy to develop dual redox active polymer electrodes for next generation all‐polymer batteries.
Dual‐ing polymers: A phenothiazine and naphthalene‐polyimide‐based redox polymer is applied as both cathode and anode material to build a symmetric polymer–polymer battery with good cycling stability for 1000 cycles at 800 mA g−1 and outstanding power density up to 1542 W kg−1.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Abstract
The practical applications of lithium metal anodes in high-energy-density lithium metal batteries have been hindered by their formation and growth of lithium dendrites. Herein, we discover ...that certain protein could efficiently prevent and eliminate the growth of wispy lithium dendrites, leading to long cycle life and high Coulombic efficiency of lithium metal anodes. We contend that the protein molecules function as a “self-defense” agent, mitigating the formation of lithium embryos, thus mimicking natural, pathological immunization mechanisms. When added into the electrolyte, protein molecules are automatically adsorbed on the surface of lithium metal anodes, particularly on the tips of lithium buds, through spatial conformation and secondary structure transformation from α-helix to β-sheets. This effectively changes the electric field distribution around the tips of lithium buds and results in homogeneous plating and stripping of lithium metal anodes. Furthermore, we develop a slow sustained-release strategy to overcome the limited dispersibility of protein in the ether-based electrolyte and achieve a remarkably enhanced cycling performance of more than 2000 cycles for lithium metal batteries.
The current Li-based battery technology is limited in terms of energy contents. Therefore, several approaches are considered to improve the energy density of these energy storage devices. Here, we ...report the combination of a heteroatom-based gel polymer electrolyte with a hybrid cathode comprising of a Li-rich oxide active material and graphite conductive agent to produce a high-energy "shuttle-relay" Li metal battery, where additional capacity is generated from the electrolyte's anion shuttling at high voltages. The gel polymer electrolyte, prepared via in situ polymerization in an all-fluorinated electrolyte, shows adequate ionic conductivity (around 2 mS cm
at 25 °C), oxidation stability (up to 5.5 V vs Li/Li
), compatibility with Li metal and safety aspects (i.e., non-flammability). The polymeric electrolyte allows for a reversible insertion of hexafluorophosphate anions into the conductive graphite (i.e., dual-ion mechanism) after the removal of Li ions from Li-rich oxide (i.e., rocking-chair mechanism).
Rechargeable sodium-sulfur (Na-S) batteries are regarded as a promising energy storage technology due to their high energy density and low cost. High-temperature sodium-sulfur (HT Na-S) batteries ...with molten sodium and sulfur as cathode materials were proposed in 1966, and later successfully commercialised for utility-scale stationary energy storage. However, their high working temperature (300-350 °C) causes some detrimental problems such as high operating costs, difficulties of maintenance (corrosion), and severe safety issues. In particular, HT Na-S batteries with Na polysulfides as the final discharge product only deliver about a third of the sulfur's theoretical capacity. These drawbacks greatly limited the broader applications of HT Na-S batteries. In recent years, extensive efforts have been devoted to developing next-generation intermediate-temperature sodium-sulfur batteries (IMT Na-S, operating at 120-300 °C) and room-temperature sodium-sulfur batteries (RT Na-S) with higher capacity, lower maintenance cost and enhanced safety. Herein, we provide a comprehensive review of the latest progress on IMT Na-S and RT Na-S batteries. We elucidate the working principles, opportunities and challenges of these non-high-temperature Na-S battery systems, and summarise the advances in the battery components including cathodes, anodes, electrolytes, and other battery constituents. In particular, the applications of solid-state electrolytes in IMT Na-S and RT Na-S chemistry are emphasised. The remaining challenges and clear perspectives are outlined for the future development of novel high-performance Na-S batteries.
We review the working mechanisms, opportunity and challenges of intermediate-temperature and room-temperature sodium-sulfur batteries for low-cost energy storage.
Rechargeable alkali metal (i.e., lithium, sodium, potassium)‐based batteries are considered as vital energy storage technologies in modern society. However, the traditional liquid electrolytes ...applied in alkali metal‐based batteries mainly consist of thermally unstable salts and highly flammable organic solvents, which trigger numerous accidents related to fire, explosion, and leakage of toxic chemicals. Therefore, exploring non‐flammable electrolytes is of paramount importance for achieving safe batteries. Although replacing traditional liquid electrolytes with all‐solid‐state electrolytes is the ultimate way to solve the above safety issues, developing non‐flammable liquid electrolytes can more directly fulfill the current needs considering the low ionic conductivities and inferior interfacial properties of existing all‐solid‐state electrolytes. Moreover, the electrolyte leakage concern can be further resolved by gelling non‐flammable liquid electrolytes to obtain quasi‐solid electrolytes. Herein, a comprehensive review of the latest progress in emerging non‐flammable liquid electrolytes, including non‐flammable organic liquid electrolytes, aqueous electrolytes, and deep eutectic solvent‐based electrolytes is provided, and systematically introduce their flame‐retardant mechanisms and electrochemical behaviors in alkali metal‐based batteries. Then, the gelation techniques for preparing quasi‐solid electrolytes are also summarized. Finally, the remaining challenges and future perspectives are presented. It is anticipated that this review will promote a safety improvement of alkali metal‐based batteries.
This review provides the latest progress in emerging non‐flammable liquid electrolytes, including non‐flammable organic liquid electrolytes, aqueous electrolytes, and deep eutectic solvent‐based electrolytes, and systematically introduce their flame‐retardant mechanisms and electrochemical behaviors in alkali metal‐based batteries. Furthermore, the gelation techniques for quasi‐solid electrolyte preparation are thoroughly summarized. This review will promote the safety improvement of alkali metal‐based batteries.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The low Coulombic efficiency and serious safety issues resulting from uncontrollable dendrite growth have severely impeded the practical applications of lithium (Li) metal anodes. Herein we report a ...stable quasi‐solid‐state Li metal battery by employing a hierarchical multifunctional polymer electrolyte (HMPE). This hybrid electrolyte was fabricated via in situ copolymerizing lithium 1‐3‐(methacryloyloxy)propylsulfonyl‐1‐(trifluoromethanesulfonyl)imide (LiMTFSI) and pentaerythritol tetraacrylate (PETEA) monomers in traditional liquid electrolyte, which is absorbed in a poly(3,3‐dimethylacrylic acid lithium) (PDAALi)‐coated glass fiber membrane. The well‐designed HMPE simultaneously exhibits high ionic conductivity (2.24×10−3 S cm−1 at 25 °C), near‐single ion conducting behavior (Li ion transference number of 0.75), good mechanical strength and remarkable suppression for Li dendrite growth. More intriguingly, the cation permselective HMPE efficiently prevents the migration of negatively charged iodine (I) species, which provides the as‐developed Li‐I batteries with high capacity and long cycling stability.
A novel hierarchical multifunctional polymer electrolyte shows near‐single ion conduction for lithium metal batteries. This electrolyte was in situ fabricated by integrating (LiMTFSI‐PETEA)‐based crosslinking gel polymer electrolyte with PDDALi‐coated glass fiber membrane. The as‐prepared multifunctional electrolyte exhibits high ionic conductivity, enhanced safety, suppression on dendrite growth, and stable cycling in lithium‐iodine batteries.
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Due to the high theoretical specific energy, the lithium-oxygen battery has been heralded as a promising energy storage system for applications such as electric vehicles. However, its large ...over-potentials during discharge-charge cycling lead to the formation of side-products, and short cycle life. Herein, we report an ionic liquid bearing the redox active 2,2,6,6-tetramethyl-1-piperidinyloxy moiety, which serves multiple functions as redox mediator, oxygen shuttle, lithium anode protector, as well as electrolyte solvent. The additive contributes a 33-fold increase of the discharge capacity in comparison to a pure ether-based electrolyte and lowers the over-potential to an exceptionally low value of 0.9 V. Meanwhile, its molecule facilitates smooth lithium plating/stripping, and promotes the formation of a stable solid electrolyte interface to suppress side-reactions. Moreover, the proportion of ionic liquid in the electrolyte influences the reaction mechanism, and a high proportion leads to the formation of amorphous lithium peroxide and a long cycling life (> 200 cycles). In particular, it enables an outstanding electrochemical performance when operated in air.
Metal ion capacitors (MICs) are foreseen to be a complementary alternative of vital importance to current energy storage issues, coupling high energy density delivered by batteries with high ...power/long cycle life offered by supercapacitors. The prime issues in realising this technology are pre-metallation and replacement of graphite electrodes that bring about an energy gain at the expense of power. Herein we present an easy-to-scale-up approach, combining activated carbon with a highly efficient and industrially compatible low-cost sacrificial salt (dimetal squarates) that can be used as a metal source for pre-metallation. Paired with a hard carbon electrode tailored to perform at high rates, lithium, sodium and potassium MICs are demonstrated. Furthermore, the successful fabrication of a lithium ion capacitor (LIC) pouch cell prototype with high energy at high power densities showing capacitance retention over 84% after 48 000 cycles validates the strategy. This breakthrough may trigger the easy and low-cost fabrication of LICs and significantly reduce technological barriers to market growth and consolidation.
A low-cost pre-metallation strategy based on inorganic sacrificial salts that decompose on the first charge.
Ambient‐temperature sodium–sulfur (Na–S) batteries are considered a promising energy storage system due to their high theoretical energy density and low costs. However, great challenges remain in ...achieving a high rechargeable capacity and long cycle life. Herein we report a stable quasi‐solid‐state Na‐S battery enabled by a poly(S‐pentaerythritol tetraacrylate (PETEA))‐based cathode and a (PETEA‐tris2‐(acryloyloxy)ethyl isocyanurate (THEICTA))‐based gel polymer electrolyte. The polymeric sulfur electrode strongly anchors sulfur through chemical binding and inhibits the shuttle effect. Meanwhile, the in situ formed polymer electrolyte with high ionic conductivity and enhanced safety successfully stabilizes the Na anode/electrolyte interface, and simultaneously immobilizes soluble Na polysulfides. The as‐developed quasi‐solid‐state Na‐S cells exhibit a high reversible capacity of 877 mA h g−1 at 0.1 C and an extended cycling stability.
Energy storage: A stable quasi‐solid‐state Na–S battery has been obtained using a poly(S‐pentaerythritol tetraacrylate (PETEA)) cathode and a (PETEA‐tris2‐(acryloyloxy)ethyl isocyanurate (THEICTA)) gel polymer electrolyte. The electrode strongly anchors sulfur by chemical binding, meanwhile the polymer electrolyte with high ionic conductivity and stable Na/electrolyte interface effectively suppresses the shuttle of polysulfides.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
High-temperature sodium-sulfur batteries operating at 300-350 °C have been commercially applied for large-scale energy storage and conversion. However, the safety concerns greatly inhibit their ...widespread adoption. Herein, we report a room-temperature sodium-sulfur battery with high electrochemical performances and enhanced safety by employing a "cocktail optimized" electrolyte system, containing propylene carbonate and fluoroethylene carbonate as co-solvents, highly concentrated sodium salt, and indium triiodide as an additive. As verified by first-principle calculation and experimental characterization, the fluoroethylene carbonate solvent and high salt concentration not only dramatically reduce the solubility of sodium polysulfides, but also construct a robust solid-electrolyte interface on the sodium anode upon cycling. Indium triiodide as redox mediator simultaneously increases the kinetic transformation of sodium sulfide on the cathode and forms a passivating indium layer on the anode to prevent it from polysulfide corrosion. The as-developed sodium-sulfur batteries deliver high capacity and long cycling stability.
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