Defects have been found to enhance the electrocatalytic performance of NiFe‐LDH for oxygen evolution reaction (OER). Nevertheless, their specific configuration and the role played in regulating the ...surface reconstruction of electrocatalysts remain ambiguous. Herein, cationic vacancy defects are generated via aprotic‐solvent‐solvation‐induced leaking of metal cations from NiFe‐LDH nanosheets. DFT calculation and in situ Raman spectroscopic observation both reveal that the as‐generated cationic vacancy defects tend to exist as VM (M=Ni/Fe); under increasing applied voltage, they tend to assume the configuration VMOH, and eventually transform into VMOH‐H which is the most active yet most difficult to form thermodynamically. Meanwhile, with increasing voltage the surface crystalline Ni(OH)x in the NiFe‐LDH is gradually converted into disordered status; under sufficiently high voltage when oxygen bubbles start to evolve, local NiOOH species become appearing, which is the residual product from the formation of vacancy VMOH‐H. Thus, we demonstrate that the cationic defects evolve along with increasing applied voltage (VM → VMOH → VMOH‐H), and reveal the essential motif for the surface restructuration process of NiFe‐LDH (crystalline Ni(OH)x → disordered Ni(OH)x → NiOOH). Our work provides insight into defect‐induced surface restructuration behaviors of NiFe‐LDH as a typical precatalyst for efficient OER electrocatalysis.
Along with increasing voltage during the OER process, the structural evolution of cationic defects within NiFe‐LDH, where the simple vacancy VM changes to VMOH and then to the most reactive VMOH‐H, and the surface restructuration, where surface crystalline Ni(OH)x is converted to disordered Ni(OH)x and then to the surface local NiOOH species, are voltage‐regulated concurrent events defining the eventual catalytic performance of the precatalyst.
Binders have been reported to play a key role in improving the cycle performance of Si anode materials of lithium‐ion batteries. In this study, the biopolymer guar gum (GG) is applied as the binder ...for a silicon nanoparticle (SiNP) anode of a lithium‐ion battery for the first time. Due to the large number of polar hydroxyl groups in the GG molecule, a robust interaction between the GG binder and the SiNPs is achieved, resulting in a stable Si anode during cycling. More specifically, the GG binder can effectively transfer lithium ions to the Si surface, similarly to polyethylene oxide solid electrolytes. When GG is used as a binder, the SiNP anode can deliver an initial discharge capacity as high as 3364 mAh g−1, with a Coulombic efficiency of 88.3% at the current density of 2100 mA g−1, and maintain a capacity of 1561 mAh g−1 after 300 cycles. The study shows that the electrochemical performance of the SiNP anode with GG binder is significantly improved compared to that of a SiNP anode with a sodium alginate binder, and it demonstrates that GG is a promising binder for Si anodes of lithium‐ion batteries.
Guar gum is used as a robust binder for a silicon nanoparticle anode of a lithium‐ion battery for the first time. With a large number of polar hydroxyl groups, the guar gum binder can provide effective transport pathways for lithium ions, which significantly improves the electrochemical performance.
Recent fruitful studies on rechargeable zinc-air battery have led to emergence of various bifunctional oxygen electrocatalysts, especially metal-based materials. However, their electrocatalytic ...configuration and evolution pathway during battery operation are rarely spotlighted. Herein, to depict the underlying behaviors, a concept named dynamic electrocatalyst is proposed. By selecting a bimetal nitride as representation, a current-driven "shell-bulk" configuration is visualized via time-resolved X-ray and electron spectroscopy analyses. A dynamic picture sketching the generation and maturation of nanoscale oxyhydroxide shell is presented, and periodic valence swings of performance-dominant element are observed. Upon maturation, zinc-air battery experiences a near two-fold enlargement in power density to 234 mW cm
, a gradual narrowing of voltage gap to 0.85 V at 30 mA cm
, followed by stable cycling for hundreds of hours. The revealed configuration can serve as the basis to construct future blueprints for metal-based electrocatalysts, and push zinc-air battery toward practical application.
Toward the pursuit of high-performance Ni2+/Co2+/Fe3+-relevant oxygen evolution reaction (OER) electrocatalysts, the modulation of local electronic structure of the active metal sites provides the ...fundamental motif, which could be achieved either through direct modifications of local chemical environment or interfacial interaction with a second metal substrate which possesses high electronegativity (typically noble metal Au). Herein, we report that the local electronic structure of Ni–Fe layered double hydroxide (LDH) could be favorably modulated through strong interfacial interactions with FeOOH nanoparticles (NPs). The biphasic and multiscale composites FeOOH/LDH demonstrated an increasingly pronounced synergy effect for OER catalysis when the average size of FeOOH NPs decreases from 18.0 to 2.0 nm. Particularly, the composite with average size of FeOOH NPs of 2.0 nm exhibited an overpotential of 174 mV at 10 mA cm–2 and a tafel slope of 27 mV dec–1 in 1.0 M KOH, outmatching all the noble and non-noble OER catalysts reported so far; it also operates smoothly in various stability tests. A mechanistic study based on XANES and EXAFS analysis, d.c. voltammetry and large amplitude Fourier Transformed a.c. voltammetry proved the presence of high-oxidation-state Fe(3+δ)+sites with relatively short Fe(3+δ)+–O bond from the highly unsaturated ultrafine FeOOH NPs which could reform the local electronic structure and favorably manipulate the electronic oxidation and thus electrocatalytic behaviors of the Ni2+ species in the Ni–Fe LDH, hence leading to the easy formation, excellent OER activity, and extraordinary structural and catalytic stability. Our work puts an emphasis on the role of the solid–solid interfacial chemistry between a Ni–Fe LDH and a non-noble-metal component in engineering the local electronic structure of the active metal sites, which successfully pushed forward the catalytic activity of the well-studied Ni–Fe LDH far beyond its current limit in OER catalysis and opened up an avenue for rational design of OER electrocatalysts.
Sodium metal anodes are poor due to the reversibility of Na plating/stripping, which hinders their practical applications. A strategy to form a sodiophilic Au–Na alloy interphase on a Cu current ...collector, involving a sputtered Au thin layer, is shown to enable efficient Na plating/stripping for a certain period of time. Herein, electrochemical behaviors of Na plating on different substrates are explored, and it is revealed that the sodiophilic interphase can be achieved universally by in situ formation of M–Na (M = Au, Sn, and Sb) alloys during Na plating prior to Na bulk deposition in the initial cycle. Moreover, it is found that repetitive alloying–dealloying leads to falling‐off of thin film sodiophilic materials and thus limits the lifespan of efficient Na cycling. Therefore, an approach is further developed by employing particles of sodiophilic materials combined with the control over the cutoff potential, which significantly improves the stability of Na plating/stripping process. Especially, the low‐cost Cu@Sn‐NPs and Cu@Sb‐MPs composite current collectors allow Na plating and stripping to cycle for 2000 and 1700 times with the average efficiency of 99.9% at 2 mA cm−2.
Stable Na plating/stripping electrochemical behaviors are achieved by using the in situ formed sodiophilic sodium‐metal (metal = Au, Sn, Sb) alloy interphase. By simultaneous control over the stripping cut‐off potential and employment of anchored metal particles, Na plating/stripping cycling is extended to 2000 times at 2 mA cm−2 with an average Coulombic efficiency of 99.9% on the sodium‐metal alloy‐based interphase.
Binders, though often used in small doses, play a crucial role in determining the electrochemical performance of lithium ion batteries with high energy density. The traditional PVDF binder, which ...interacts with electrode materials via weak Van der Waals forces and consequently lacks the necessary capabilities (e.g., the suppression of significant volume variations, the interface maintenance etc.), could not fulfill the high demands of batteries with high energy density. Besides, extensive usage of the PVDF binder in the lithium ion battery is cost‐ineffective and may raise environmental concerns as its handling often needs the assistance of organic solvents. Herein, recent progresses on the development of novel eco‐friendly, low‐cost and water‐soluble binders which recently have gained increasing attention as a promising performance booster for lithium ion batteries with high energy density are reviewed. Such water soluble polymer binders are either natural, or modified, or synthesized, and they were observed with profoundly enhanced chemical/physical interactions with the electrode materials, stronger mechanical adhesion and evidently improved volume variation durability, leading to dramatic improvements in the electrochemical performances of Si‐based anodes, spinel/layered oxide cathodes and S cathodes. Perspectives for future research directions on water soluble binders are also discussed.
Water soluble polymer binders with profoundly enhanced chemical/physical interactions with the electrode materials, stronger mechanical adhesion and evidently improved volume variation durability, leading to dramatic improvements in the electrochemical performances of Si‐based anodes, spinel/layered oxide cathodes and S cathodes.
A cathode for high‐rate performance lithium‐ion batteries (LIBs) has been developed from a crystal habit‐tuned nanoplate Li(Li0.17Ni0.25Mn0.58)O2 material, in which the proportion of (010) nanoplates ...(see figure) has been significantly increased. The results demonstrate that the fraction of the surface that is electrochemically active for Li+ transportation is a key criterion for evaluating the different nanostructures of potential LIB materials.
Li metal is considered as an ideal anode for Li‐based batteries. Unfortunately, the growth of Li dendrites during cycling leads to an unstable interface, a low coulombic efficiency, and a limited ...cycling life. Here, a novel approach is proposed to protect the Li‐metal anode by using a uniform agarose film. This natural biopolymer film exhibits a high ionic conductivity, high elasticity, and chemical stability. These properties enable a fast Li‐ion transfer and feasiblity to accomodate the volume change of Li metal, resulting in a dendrite‐free anode and a stable interface. Morphology characterization shows that Li ions migrate through the agarose film and then deposit underneath it. A full cell with the cathode of LiFPO4 and an anode contaning the agarose film exhibits a capacity retention of 87.1% after 500 cycles, much better than that with Li foil anode (70.9%) and Li‐deposited Cu anode (5%). This study provides a promising strategy to eliminate dendrites and enhance the cycling ability of lithium‐metal batteries through coating a robust artificial film of natural biopolymer on lithium‐metal anode.
Agarose, a kind of natural biopolymer, is used to construct artificial protective film for the Li‐metal anode. Li ions can diffuse through and deposit under this film, leading to a dendrite‐free surface during repeated Li plating/stripping processes. This film can also reduce the side reaction due to its function as a physical barrier to separate the electrolyte and Li metal.
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