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.
Long Hard Road: The Lithium-Ion Battery and the Electric
Car provides an inside look at the birth of the lithium-ion
battery, from its origins in academic labs around the world to its
transition to ...its new role as the future of automotive power. It
chronicles the piece-by-piece development of the battery, from its
early years when it was met by indifference from industry to its
later emergence in Japan where it served in camcorders, laptops,
and cell phones. The book is the first to provide a glimpse inside
the Japanese corporate culture that turned the lithium-ion
chemistry into a commercial product. It shows the intense race
between two companies, Asahi Chemical and Sony Corporation, to
develop a suitable anode. It also explains, for the first time, why
one Japanese manufacturer had to build its first preproduction
cells in a converted truck garage in Boston, Massachusetts.
Building on that history, Long Hard Road then takes
readers inside the auto industry to show how lithium-ion solved the
problems of earlier battery chemistries and transformed the
electric car into a viable competitor. Starting with the Henry Ford
and Thomas Edison electric car of 1914, it chronicles a long list
of automotive failures, then shows how a small California car
converter called AC Propulsion laid the foundation for a revolution
by packing its car with thousands of tiny lithium-ion cells. The
book then takes readers inside the corporate board rooms of Detroit
to show how mainstream automakers finally decided to adopt
lithium-ion.
Long Hard Road is unique in its telling of the
lithium-ion tale, revealing that the battery chemistry was not the
product of a single inventor, nor the dream of just three Nobel
Prize winners, but rather was the culmination of dozens of
scientific breakthroughs from many inventors whose work was united
to create a product that ultimately changed the world.
Fast lithium ion transport with a high current density is critical for thick sulfur cathodes, stemming mainly from the difficulties in creating effective lithium ion pathways in high sulfur content ...electrodes. To develop a high‐rate cathode for lithium–sulfur (Li–S) batteries, extenuation of the lithium ion diffusion barrier in thick electrodes is potentially straightforward. Here, a phyllosilicate material with a large interlamellar distance is demonstrated in high‐rate cathodes as high sulfur loading. The interlayer space (≈1.396 nm) incorporated into a low lithium ion diffusion barrier (0.155 eV) significantly facilitates lithium ion diffusion within the entire sulfur cathode, and gives rise to remarkable nearly sulfur loading‐independent cell performances. When combined with 80% sulfur contents, the electrodes achieve a high capacity of 865 mAh g−1 at 1 mA cm−2 and a retention of 345 mAh g−1 at a high discharging/charging rate of 15 mA cm−2, with a sulfur loading up to 4 mg. This strategy represents a major advance in high‐rate Li–S batteries via the construction of fast ions transfer paths toward real‐life applications, and contributes to the research community for the fundamental mechanism study of loading‐independent electrode systems.
Lithium‐montmorillonite with atomic interlamellar ion paths is reported as a high‐sulfur‐content host for high‐rate and stable lithium–sulfur (Li–S) batteries. The interlayer space (≈1.396 nm) of lithium‐montmorillonite facilitates lithium‐ion diffusion within the entire sulfur cathode, and gives rise to remarkable nearly sulfur‐loading‐independent cell performances. This work provides valuable insights into the commercial applications of high‐energy Li–S batteries.
Lithium‐metal batteries (LMBs), as one of the most promising next‐generation high‐energy‐density storage devices, are able to meet the rigid demands of new industries. However, the direct utilization ...of metallic lithium can induce harsh safety issues, inferior rate and cycle performance, or anode pulverization inside the cells. These drawbacks severely hinder the commercialization of LMBs. Here, an up‐to‐date review of the behavior of lithium ions upon deposition/dissolution, and the failure mechanisms of lithium‐metal anodes is presented. It has been shown that the primary causes consist of the growth of lithium dendrites due to large polarization and a strong electric field at the vicinity of the anode, the hyperactivity of metallic lithium, and hostless infinite volume changes upon cycling. The recent advances in liquid organic electrolyte (LOE) systems through modulating the local current density, anion depletion, lithium flux, the anode–electrolyte interface, or the mechanical strength of the interlayers are highlighted. Concrete strategies including tailoring the anode structures, optimizing the electrolytes, building artificial anode–electrolyte interfaces, and functionalizing the protective interlayers are summarized in detail. Furthermore, the challenges remaining in LOE systems are outlined, and the future perspectives of introducing solid‐state electrolytes to radically address safety issues are presented.
Dendrite growth, continuous side reactions, and infinite volume changes inside a lithium‐metal anode severely hamper its application in high‐energy batteries. Concrete failure mechanisms and effective strategies, including lowering the local current density, reducing anion depletion, smoothing interfaces, reshaping the lithium‐ion flux, and mechanically blocking dendrites, are comprehensively reviewed.
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 (LiN3) 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 (LiNO3).
The bright azide of life: Lithium azide effectively favors the formation of dendrite‐free and highly ionic conductive solid electrolyte interphases on Li electrodes, and thereby improves the cycling performances and sulfur utilization of Li–S cells.
Silicon (Si) and lithium metal are the most favorable anodes for high‐energy‐density lithium‐based batteries. However, large volume expansion and low electrical conductivity restrict ...commercialization of Si anodes, while dendrite formation prohibits the applications of lithium‐metal anodes. Here, uniform nanoporous Si@carbon (NPSi@C) from commercial alloy and CO2 is fabricated and tested as a stable anode for lithium‐ion batteries (LIBs). The porosity of Si as well as graphitization degree and thickness of the carbon layer can be controlled by adjusting reaction conditions. The rationally designed porosity and carbon layer of NPSi@C can improve electronic conductivity and buffer volume change of Si without destroying the carbon layer or disrupting the solid electrolyte interface layer. The optimized NPSi@C anode shows a stable cyclability with 0.00685% capacity decay per cycle at 5 A g−1 over 2000 cycles for LIBs. The energy storage mechanism is explored by quantitative kinetics analysis and proven to be a capacitance‐battery dual model. Moreover, a novel 2D/3D structure is designed by combining MXene and NPSi@C. As lithiophilic nucleation seeds, NPSi@C can induce uniform Li deposition with buffered volume expansion, which is proven by exploring Li‐metal deposition morphology on Cu foil and MXene@NPSi@C. The practical potential application of NPSi@C and MXene@NPSi@C is evaluated by full cell tests with a Li(Ni0.8Co0.1Mn0.1)O2 cathode.
Uniform nanoporous Si@carbon (NPSi@C) from commercial alloy and CO2 is fabricated as an anode for lithium‐ion batteries. The porosity of Si, graphitization degree, and thickness of carbon layer can be controlled by adjusting reaction conditions. Moreover, a 2D/3D structure is designed by combining MXene and NPSi@C. As lithiophilic nucleation seeds for Li‐metal anode, NPSi@C can induce uniform Li deposition with buffered volume expansion.
Based on 19 high-quality articles, this Special Issue presents methods for further improving the currently achievable recycling rate, product quality in terms of focused elements, and approaches for ...the enhanced mobilization of lithium, graphite, and electrolyte components. In particular, the target of early-stage Li removal is a central point of various research approaches in the world, which has been reported, for example, under the names early-stage lithium recovery (ESLR process) with or without gaseous CO2 and supercritical CO2 leaching (COOL process). Furthermore, many more approaches are present in this Special Issue, ranging from robotic disassembly and the dismantling of Li‐ion batteries, or the optimization of various pyro‐ and hydrometallurgical as well as combined battery recycling processes for the treatment of conventional Li‐ion batteries, all the way to an evaluation of the recycling on an industrial level. In addition to the consideration of Li distribution in compounds of a Li2O-MgO-Al2O3-SiO2-CaO system, Li recovery from battery slags is also discussed. The development of suitable recycling strategies of six new battery systems, such as all-solid-state batteries, but also lithium–sulfur batteries, is also taken into account here. Some of the articles also discuss the fact that battery recycling processes do not have to produce end products such as high-purity battery materials, but that the aim should be to find an “entry point” into existing, proven large-scale industrial processes. Participants in this Special Issue originate from 18 research institutions from eight countries.
Compared to traditional lithium‐ion batteries with liquid electrolytes, all‐solid‐state lithium batteries have attracted extensive attention due to their heightened safety and energy density. Lithium ...argyrodite materials are promising solid electrolytes (SE) due to their high ionic conductivity, low grain boundary resistance, and favorable mechanical properties. However, the poor chemical/electrochemical stability of lithium argyrodite electrolytes toward the bare lithium metal anode inhibits their applications in all‐solid‐state lithium metal batteries (ASSLMBs). Here, Li‐SnF2 composite anodeswas used to induce the formation of solid electrolyte interphase (SEI) composed of LiCl, LiF, and Li22Sn5 at the Li/SE interface. The high interface energy barriers for LiF and LiCl induces the uniform deposition of lithium ions, thus hindering the growth of lithium dendrites. Meanwhile, the fast Li‐ion diffusion coefficient of the Li22Sn5 alloy accelerates Li‐ion migration across the interface section. The symmetrical cell exhibits stable cycling performance over long durations over 300 h at 0.5 mA cm−2. Moreover, the LiNbO3@NCM712/Li5.5PS4.5Cl1.5/Li‐10%SnF2 battery delivers a high initial discharge capacity of 170.9 mAh g−1 at 0.1C and retains 72.9% of its original capacity after 500 cycles at 0.5C. The facial approach for Li‐SnF2 composite anode enables the production of ASSLMBs with superior electrochemical performance.
The growth of lithium dendrites hinders the practical feasibility of ASSLMBs. SnF2 induces the formation of SEI composed of LiCl, Li22Sn5 and LiF at the Li/SE interface. LiF and LiCl with high interface energy barrier inhibit dendrite growth, while Li22Sn5 alloy accelerates the migration of Li+ at the interface, achieving good lithium metal compatibility.
PDF
