Lithium‐ion batteries, which have revolutionized portable electronics over the past three decades, were eventually recognized with the 2019 Nobel Prize in chemistry. As the energy density of current ...lithium‐ion batteries is approaching its limit, developing new battery technologies beyond lithium‐ion chemistry is significant for next‐generation high energy storage. Lithium–sulfur (Li–S) batteries, which rely on the reversible redox reactions between lithium and sulfur, appears to be a promising energy storage system to take over from the conventional lithium‐ion batteries for next‐generation energy storage owing to their overwhelming energy density compared to the existing lithium‐ion batteries today. Over the past 60 years, especially the past decade, significant academic and commercial progress has been made on Li–S batteries. From the concept of the sulfur cathode first proposed in the 1960s to the current commercial Li–S batteries used in unmanned aircraft, the story of Li–S batteries is full of breakthroughs and back tracing steps. Herein, the development and advancement of Li–S batteries in terms of sulfur‐based composite cathode design, separator modification, binder improvement, electrolyte optimization, and lithium metal protection is summarized. An outlook on the future directions and prospects for Li–S batteries is also offered.
The major developments and advancements of lithium–sulfur batteries over the past 60 years are presented. The prospects and an outlook on the future development of lithium–sulfur batteries for large‐scale practical applications are also discussed and presented.
Lithium sulfur (Li–S) batteries are attracting ever‐increasing interests as a new generation rechargeable battery system with high energy density and low cost. Li–S batteries will fulfill their ...theoretical potential if the problem of polysulfides shuttle effect can be solved. Therefore, tremendous efforts have been devoted to overcoming this problem from the aspects of physical confinement and chemisorption of polysulfides. Recently, it is discovered that replacing sulfur cathodes with lithium sulfide (Li2S) can not only largely avoid the volume expansion issue during cycling, but it can also work with anode materials other than lithium metal to eliminate serious safety concerns for traditional Li–S batteries. However, there are many challenges for developing practical Li metal‐free Li–S battery systems, because Li2S‐based cathode materials are moisture‐sensitive and prelithiation of the non‐Li metal anode materials is usually required for practical applications. This study reviews the recent advances of Li‐S batteries based on Li2S cathode with features of improved safety, high Coulombic efficiency, and high energy density. The electrode activation processes are also discussed, which is critical for achieving high performances. It is anticipated that the extensive efforts will lead to breakthroughs for the development of Li2S cathode ‐based Li‐S batteries.
Herein, the recent advances of lithium‐sulfur batteries based on Li2S cathode coupled with Li‐free anodes or protected Li anodes, which have features of improved safety, high Coulombic efficiency and high energy density, are reviewed. It is anticipated that the extensive efforts will lead to breakthroughs for the development of lithium‐sulfur batteries based on Li2S cathode.
Selenium cathodes have attracted considerable attention due to high electronic conductivity and volumetric capacity comparable to sulphur cathodes. However, practical development of lithium-selenium ...batteries has been hindered by the low selenium reaction activity with lithium, high volume changes and rapid capacity fading caused by the shuttle effect of polyselenides. Recently, single atom catalysts have attracted extensive interests in electrochemical energy conversion and storage because of unique electronic and structural properties, maximum atom-utilization efficiency, and outstanding catalytic performances. In this work, we developed a facile route to synthesize cobalt single atoms/nitrogen-doped hollow porous carbon (Co
-HC). The cobalt single atoms can activate selenium reactivity and immobilize selenium and polyselenides. The as-prepared selenium-carbon (Se@Co
-HC) cathodes deliver a high discharge capacity, a superior rate capability, and excellent cycling stability with a Coulombic efficiency of ~100%. This work could open an avenue for achieving long cycle life and high-power lithium-selenium batteries.
Rechargeable multivalent metal (e.g., Ca, Mg or, Al) batteries are ideal candidates for large-scale electrochemical energy storage due to their intrinsic low cost. However, their practical ...application is hampered by the low electrochemical reversibility, dendrite growth at the metal anodes, sluggish multivalent-ion kinetics in metal oxide cathodes and, poor electrode compatibility with non-aqueous organic-based electrolytes. To circumvent these issues, here we report various aqueous multivalent-ion batteries comprising of concentrated aqueous gel electrolytes, sulfur-containing anodes and, high-voltage metal oxide cathodes as alternative systems to the non-aqueous multivalent metal batteries. This rationally designed aqueous battery chemistry enables satisfactory specific energy, favorable reversibility and improved safety. As a demonstration model, we report a room-temperature calcium-ion/sulfur| |metal oxide full cell with a specific energy of 110 Wh kg
and remarkable cycling stability. Molecular dynamics modeling and experimental investigations reveal that the side reactions could be significantly restrained through the suppressed water activity and formation of a protective inorganic solid electrolyte interphase. The unique redox chemistry of the multivalent-ion system is also demonstrated for aqueous magnesium-ion/sulfur||metal oxide and aluminum-ion/sulfur||metal oxide full cells.
Amorphous TiO2@C nanospheres were synthesized via a template approach. After being sintered under different conditions, two types of polyphase TiO2 hollow nanospheres were obtained. The ...electrochemical properties of the amorphous TiO2 nanospheres and the TiO2 hollow nanospheres with different phases were characterized as anodes for the Na-ion batteries. It was found that all the samples demonstrated excellent cyclability, which was sustainable for hundreds of cycles with little capacity fading, although the anatase TiO2 presented a capability that was better than that of the mixed anatase/rutile TiO2 or the amorphous TiO2@C. Through crystallographic analysis, it was revealed that the anatase TiO2 crystal structure supplies two-dimensional diffusion paths for Na-ion intercalation and more accommodation sites. Density functional theory calculations indicated lower energy barriers for the insertion of Na+ into anatase TiO2. Therefore, anatase TiO2 hollow nanospheres show excellent high-rate performance. Through ex situ field emission scanning electron microscopy, it was revealed that the TiO2 hollow nanosphere architecture can be maintained for hundreds of cycles, which is the main reason for its superior cyclability.
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.
Rational design and controllable synthesis of TiO2 based materials with unique microstructure, high reactivity, and excellent electrochemical performance for lithium ion batteries are crucially ...desired. In this paper, we developed a versatile route to synthesize hollow TiO2/graphitic carbon (H-TiO2/GC) spheres with superior electrochemical performance. The as-prepared mesoporous H-TiO2/GC hollow spheres present a high specific surface area (298 m2 g–1), a high pore volume (0.31 cm3 g–1), a large pore size (∼5 nm), well-defined hollow structure (monodispersed size of 600 nm and inner diameter of ∼400 nm, shell thickness of 100 nm), and small nanocrystals of anatase TiO2 (∼8 nm) conformably encapsulated in ultrathin graphitic carbon layers. As a result, the H-TiO2/GC hollow spheres achieve excellent electrochemical reactivity and stability as an anode material for lithium ion batteries. A high specific capacity of 137 mAh g–1 can be achieved up to 1000 cycles at a current density of 1 A g–1 (5 C). We believe that the mesoporous H-TiO2/GC hollow spheres are expected to be applied as a high-performance electrode material for next generation lithium ion batteries.
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