Lithium (Li) metal is a promising anode material for high‐energy density batteries. However, the unstable and static solid electrolyte interphase (SEI) can be destroyed by the dynamic Li ...plating/stripping behavior on the Li anode surface, leading to side reactions and Li dendrites growth. Herein, we design a smart Li polyacrylic acid (LiPAA) SEI layer high elasticity to address the dynamic Li plating/stripping processes by self‐adapting interface regulation, which is demonstrated by in situ AFM. With the high binding ability and excellent stability of the LiPAA polymer, the smart SEI can significantly reduce the side reactions and improve battery safety markedly. Stable cycling of 700 h is achieved in the LiPAA‐Li/LiPAA‐Li symmetrical cell. The innovative strategy of self‐adapting SEI design is broadly applicable, providing opportunities for use in Li metal anodes
Stretching exercises: A flexible lithium polyacrylic acid (LiPAA) solid electrolyte interphase (SEI) layer which is highly stretchable is designed to address the dynamic volume changes during Li plating/stripping on the Li anode surface in Li ion batteries. The LiPAA polymer SEI can significantly reduce the side reactions and improve the safety performance.
A hybrid solid/liquid electrolyte with superior security facilitates the implementation of high‐energy‐density storage devices, but it suffers from inferior chemical compatibility with cathodes. ...Herein, an optimal lithium difluoro(oxalato)borate salt was introduced to build in situ an amorphous cathode electrolyte interphase (CEI) between Ni‐rich cathodes and hybrid electrolyte. The CEI preserves the surface structure with high compatibility, leading to enhanced interfacial stability. Meanwhile, the space‐charge layer can be prominently mitigated at the solid/solid interface via harmonized chemical potentials, acquiring promoted interfacial dynamics as revealed by COMSOL simulation. Consequently, the amorphous CEI integrates the bifunctionality to provide an excellent cycling stability, high Coulombic efficiency, and favorable rate capability in high‐voltage Li‐metal batteries, innovating the design philosophy of functional CEI strategy for future high‐energy‐density batteries.
The CEI's advantage: An amorphous cathode electrolyte interphase (CEI) with superior chemical compatibility and plasticity was formed via in situ LiDFOB conversion. It endows high‐voltage hybrid solid/liquid batteries with significantly enhanced interfacial stability, durability, and dynamics.
Li–CO2 batteries arouse great interest in the context of carbon neutralization, but their practicability is severely hindered by the sluggish CO2 redox reaction kinetics at the cathode, which brings ...about formidable challenges such as high overpotential and low Coulombic efficiency. For the complex multi‐electron transfer process, the design of catalysts at the molecular or atomic level and the understanding of the relationship between electron state and performance are essential for the CO2 redox. However, little attention is paid to it. In this work, using Co3S4 as a model system, density functional theory (DFT) calculations reveal that the adjusted d‐band and p‐band centers of Co3S4 with the introduction of Cu and sulfur vacancies are hybridized between CO2 and Li species, respectively, which is conducive to the adsorption of reactants and the decomposition of Li2CO3, and the experimental results further verify the effectiveness of energy band engineering. As a result, a highly efficient bidirectional catalyst is produced and shows an ultra‐small voltage gap of 0.73 V and marvelous Coulombic efficiency of 92.6%, surpassing those of previous catalysts under similar conditions. This work presents an effective catalyst design and affords new insight into the high‐performance cathode catalyst materials for Li–CO2 batteries.
For the Li–CO2 batteries, the design of catalysts at the molecular or atomic level and understanding of the relationship between structure and performance are essential. Under the guidance of energy band engineering, a highly efficient catalyst is designed and shows obvious bidirectional effect for CO2 redox. This work offers new avenues for designing excellent electrocatalysts in Li–CO2 batteries.
Lithium‐carbon dioxide (Li‐CO2) batteries are regarded as a prospective technology to relieve the pressure of greenhouse emissions but are confronted with sluggish CO2 redox kinetics and low energy ...efficiency. Developing highly efficient and low‐cost catalysts to boost bidirectional activities is craved but remains a huge challenge. Herein, derived from the spent lithium‐ion batteries, a tandem catalyst is subtly synthesized and significantly accelerates the CO2 reduction and evolution reactions (CO2RR and CO2ER) kinetics with an in‐built electric field (BEF). Combining with the theoretical calculations and advanced characterization techniques, this work reveals that the designed interface‐induced BEF regulates the adsorption/decomposition of the intermediates during CO2RR and CO2ER, endowing the recycled tandem catalyst with excellent bidirectional activities. As a result, the spent electronics‐derived tandem catalyst exhibits remarkable bidirectional catalytic performance, such as an ultralow voltage gap of 0.26 V and an ultrahigh energy efficiency of 92.4%. Profoundly, this work affords new opportunities to fabricate low‐cost electrocatalysts from recycled spent electronics and inspires fresh perceptions of interfacial regulation including but not limited to BEF to engineer better Li‐CO2 batteries.
One critical challenge of lithium‐carbon dioxide (Li‐CO2) batteries is to develop highly efficient and low‐cost catalysts with precise structure. A tandem catalyst with an in‐built electric field is elaborately recycled from the spent batteries and exhibits remarkable bidirectional activities. This work affords new opportunities to fabricate low‐cost electrocatalysts and inspires fresh perceptions of interfacial regulation to engineer better Li‐CO2 batteries.
Rechargeable lithium‐metal batteries (RLBs), which employ the Li‐metal anode to acquire notably boosted specific energy at cell level, represent the “Holy Grail” for “beyond Li‐ion” electrochemical ...energy storage technology. Currently, the practical use of RLBs is impeded by poor cycling and safety performance, which are derived from high chemical reactivity of metallic Li and uncontrollable formation and propagation of metal dendrites during repeated Li plating/stripping. In this study, a new strategy is demonstrated to stabilize the anode electrochemistry of RLBs by applying a Mg3N2‐decorated functional separator onto the Li‐metal surface. An in situ conversion‐alloying reaction occurring at Li‐separator interface assists formation of a mixed ion/electron conducting layer that consists mainly of Li3N and Li‐Mg solid‐solution. The inorganic interlayer effectively suppresses parasitic reactions at Li‐electrolyte interface while simultaneously homogenizes Li+/e‐ flux across the interface and therefore, contributes to dendrite‐free operation of Li‐metal anode. A Li||LiNi0.6Co0.2Mn0.2O2 battery based on the functional separator delivers a reversible capacity of 129 mAh g‐1 after 600 cycles at 0.5 C, which corresponds to a capacity retention of 75.9%. The preparation of functional separator is scalable and adaptive to battery manufacture, which brings new opportunities to realize high‐energy RLBs with long cycle life and improved safety.
A mixed ion/electron conducting layer is in situ formed at the interface between Li‐metal anode and Mg3N2‐supported functional separator, which enables fast Li+ diffusion, uniform Li plating, and inhibits interfacial parasitic reactions for dendrite‐free operation of high‐energy rechargeable Li‐metal batteries.
High-energy rechargeable Li metal batteries are hindered by dendrite growth due to the use of a liquid electrolyte. Solid polymer electrolytes, as promising candidates to solve the above issue, are ...expected to own high Li ion conductivity without sacrificing mechanical strength, which is still a big challenge to realize. In this study, a bifunctional solid polymer electrolyte exactly having these two merits is proposed with an interpenetrating network of poly(ether–acrylate) (ipn-PEA) and realized via photopolymerization of ion-conductive poly(ethylene oxide) and branched acrylate. The ipn-PEA electrolyte with facile processing capability integrates high mechanical strength (ca. 12 GPa) with high room-temperature ionic conductance (0.22 mS cm–1), and significantly promotes uniform Li plating/stripping. Li metal full cells assembled with ipn-PEA electrolyte and cathodes within 4.5 V vs Li+/Li operate effectively at a rate of 5 C and cycle stably at a rate of 1 C at room temperature. Because of its fabrication simplicity and compelling characteristics, the bifunctional ipn-PEA electrolyte reshapes the feasibility of room-temperature solid-state Li metal batteries.
Reversible and dendrite‐free zinc (Zn) circulation is essential for longevous aqueous zinc‐ion batteries (ZIBs) and greatly impacted by the property of Zn interface and electrolyte, especially when ...confronted with high current density and large area capacity. Herein, a hierarchical Zn interface is constructed by the preferential anion surfactant adsorption and reaction, and assists to reduce the interfacial energy and side reactions for enhanced diffusion kinetics and reversibility during Zn plating/stripping. Thus, highly reversible and smooth Zn anodes are achieved with a long‐term stability of 5500 h at 1 mA cm−2/1 mAh cm−2, an impressive rate up to 40 mA cm−2 for 10 mAh cm−2 and a large cumulative plating capacity of 4.45 Ah cm−2 at 10 mA cm−2 in Zn symmetric cells. Even under a high depth of discharge of 60% (5.85/7.65 mAh cm−2), Zn symmetric batteries can still maintain ca. 800 h's life. The proposed countermeasure has also proved to be valid in prolonging the lifespan and stability of Zn‐MnO2 full batteries at both low and high cycling current densities.
An interfacial regulation strategy of preferential adsorption via anionic surfactants, 2‐acrylamide‐2‐methylpropanesulfonic (AMPS), is proposed to reduce side reactions and enhance the diffusion kinetics of zinc‐ion at the zinc/electrolyte interface, thereby achieving highly reversible and flat zinc anode at large area capacity and depth of discharge.
Lithium metal has been deemed as the most attractive anode due to its high theoretical capacity and low anode potential. Unfortunately, its development still faces various challenges, including ...dendritic Li growth and low Coulombic efficiency. Here, we demonstrate that a light-weight, flexible, and free-standing 3D hollow carbon fiber (3D-HCF) container with high electroactive surface area can significantly reduce local current density and improve the Li deposition behavior. Li is confined within the interspace among the fibers and inside the hollow tubular fibers without uncontrollable Li dendrites. The Li anode in the 3D-HCFs exhibits high Coulombic efficiency (∼99.5% over 350 cycles), large areal capacity, and long-running lifespan (>1,200 hr) with an exceptionally low overpotential (<20 mV). A full cell with a LiFePO4 cathode shows flat voltage profiles and good cycle life. We expect this work to inspire other Li container designs to promote the development of Li metal anodes.
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•A flexible and free-standing 3D hollow carbon fiber container was constructed•The container with porous skeleton can accommodate Li and suppress Li dendrite growth•High Coulombic efficiency, large areal capacity, and long lifespan can be achieved•A full cell with a LiFePO4 cathode shows flat voltage profiles and good cycle life
Li metal anodes have inspired ever-increasing interest in high-energy-density batteries due to the high theoretical capacity and low anode potential. However, their application still faces various significant challenges, especially dendritic lithium growth, which would have serious safety concerns and poor electrochemical performance. Here, we demonstrate that a light-weight, flexible, and free-standing 3D hollow carbon fiber container with high electroactive surface area can significantly improve the electrochemical deposition behavior of Li. By confining Li within the interspace among the fibers and the inner hollow space of the tubular fibers, dendrite-free plating/stripping, high and stable Coulombic efficiency (∼99.5% over 350 cycles), large areal capacity, and long-running lifespan (>1,200 hr) can be achieved. We expect this work to inspire other 3D current collector designs to accommodate large areal capacity Li without Li dendrites for high-energy-density batteries.
Lithium metal has been deemed the most attractive anode for high-energy-density batteries due to its high theoretical capacity and low anode potential. Unfortunately, its development still faces various challenges, mainly including dendritic Li growth and low Coulombic efficiency. Here, we constructed a flexible and free-standing 3D hollow carbon fiber container with porous skeleton, which can suppress Li dendrite growth and bring about high Coulombic efficiency, large areal capacity, long lifespan, and good full cell performance.
The fast-ionic-conducting ceramic electrolyte is promising for next-generation high-energy-density Li-metal batteries, yet its application suffers from the high interfacial resistance and poor ...interfacial stability. In this study, the compatible solid-state electrolyte was designed by coating Li1.4Al0.4Ti1.6(PO4)3 (LATP) with polyacrylonitrile (PAN) and polyethylene oxide (PEO) oppositely to satisfy deliberately the disparate interface demands. Wherein, the upper PAN constructs soft-contact with LiNi0.6Mn0.2Co0.2O2, and the lower PEO protects LATP from being reduced, guaranteeing high-voltage tolerance and improved stability toward Li-metal anode performed in one ceramic. Moreover, the core function of LATP is amplified to guide homogeneous ions distribution and hence suppresses the formation of a space-charge layer across interfaces, uncovered by the COMSOL Multiphysics concentration field simulation. Thus, such a bifunctional modified ceramic electrolyte integrates the respective superiority to render Li-metal batteries with excellent cycling stability (89% after 120 cycles), high Coulombic efficiency (exceeding 99.5% per cycle), and a dendrite-free Li anode at 60 °C, which represents an overall design of ceramic interface engineering for future practical solid battery systems.
Electrochemical energy storage has experienced unprecedented advancements in recent years and extensive discussions and reviews on the progress of multivalent metal‐ion batteries have been made ...mainly from the aspect of electrode materials, but relatively little work comprehensively discusses and provides an outlook on the development of electrolytes in these systems. Under this circumstance, this Review will initially introduce different types of electrolytes in current multivalent metal‐ion batteries and explain the basic ion conduction mechanisms, preparation methods, and pros and cons. On this basis, we will discuss in detail the research and development of electrolytes for multivalent metal‐ion batteries in recent years, and finally, critical challenges and prospects for the application of electrolytes in multivalent metal‐ion batteries will be put forward.
Electrolytes for Multivalent Batteries: This work focuses on different types of electrolytes and their latest applications in zinc, magnesium, calcium, and aluminum‐ion batteries, and discusses the development direction and prospect of various metal‐ion battery electrolytes.
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