RESUMO
Chloride-ion batteries (CIBs) have drawn growing attention in large-scale energy storage applications owing to their comprehensive merits of high theoretical energy density, dendrite-free characteristic, and abundance of chloride-containing materials. Nonetheless, cathodes for CIBs are plagued by distinct volume effect and sluggish Cl- diffusion kinetics, leading to inferior rate capability and short cycling life. Herein, an unconventional Ni5 Ti-Cl LDH is reported with a high nickel ratio as a cathode material for CIB. The reversible capacity of Ni5 Ti-Cl LDH retains 127.9 mAh g-1 over 1000 cycles at a large current density of 1000 mA g-1 , which exceeds that of ever reported CIBs, with extraordinary low volume change of 1.006% during a whole charge/discharge process. Such superior Cl-storage performance is attributed to synergetic contributions consisting of high redox activity from Ni2+ /Ni3+ and pinning Ti that restrains local structural distortion of LDH host layers and enhances adsorption intensity of chloride atoms during the reversible Cl- intercalation/de-intercalation in LDH gallery, which are revealed by a comprehensive study including X-ray photoelectron spectroscopy, kinetic investigations, and DFT calculations. This work provides an effective strategy to design low-cost LDHs materials for high-performance CIBs, which are also applicable to other types of halide-ion batteries (e.g., fluoride-ion and bromide-ion batteries).
RESUMO
Aqueous chloride-ion batteries (ACIBs) with environmental friendliness and high safety hold great potential to fulfill the green energy demand for ocean desalination. Herein, for the first time, a composite consisting of Cl--intercalated CoFe layered double hydroxides (CoFe-Cl-LDH) cross-linked with CNTs (CoFe-Cl-LDH/CNT) is synthesized and demonstrated to be a novel high-performance anode for ACIBs in a neutral NaCl aqueous solution. While exhibiting a high initial capacity of â¼190 mAh g-1 at 200 mA g-1, CoFe-Cl-LDH/CNT is capable of delivering a reversible capacity of â¼125 mAh g-1 after 200 cycles. At a high current density of 400 mA g-1, it still holds a capacity of â¼120 mAh g-1. The excellent Cl- storage performance can be contributed to the unique topochemical transformation feature that reverses intercalation/deintercalation of Cl- along with valence changes of Co2+/Co3+ and Fe2+/Fe3+ during charge/discharge and the improved electronic conductivity by hybridizing with CNTs. It is interesting that the invertible insertion/extraction of interlayer H2O was discovered, which could be beneficial to the capacity after cycles to a certain extent. The Cl--intercalated LDH material declared in this work shows its feasibility on Cl- capture/release in aqueous anion-type batteries and provides a new opportunity for future development of ACIBs or aqueous desalination technology.
RESUMO
A carbonate intercalated magnesium aluminum layered double hydroxide is used as an anode material for lithium-ion batteries, displaying a maximum discharge specific capacity of 814 mA h g-1 at 200 mA g-1 in this work through utilizing the valence variation of Mg and the conversion between LiOH and LiH/Li2O.
RESUMO
Layered double hydroxides (LDHs) have been intensively investigated as promising cathodes for the new concept chloride ion battery (CIB) with multiple advantages of high theoretical energy density, abundant raw materials and unique dendrite-free characteristics. However, driven by the great compositional diversity, a complete understanding of interactions between metal cations, as well as a synergetic effect between metal cations and lattice oxygen on LDH host layers in terms of the reversible Cl-storage capability, is still a crucial but elusive issue. In this work, we synthesized a series of chloride-inserted trinary Mox-doped NiCo2-Cl LDH (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) with gradient oxygen vacancies as enhanced cathodes toward CIBs. The combination of advanced spectroscopic techniques and theoretical calculations reveals that the Mo dopant facilitates oxygen vacancy formation and varies the valence states of coordinated transition metals, which can not only tune the electronic structure effectively and promote Cl-ion diffusion, but improve the redox activity of LDHs. The optimized Mo0.3NiCo2-Cl LDH delivers a reversible discharge capacity of 159.7 mA h g-1 after 300 cycles at 150 mA g-1, which is almost a triple enhancement compared to that of NiCo2Cl LDH. The superior Cl-storage of trinary Mo0.3NiCo2Cl LDH is attributed to the reversible intercalation/deintercalation of chloride ions in the LDH gallery along with the oxidation state changes in Ni0/Ni2+/Ni3+, Co0/Co2+/Co3+ and Mo4+/Mo6+ couples. This simple vacancy engineering strategy provides critical insights into the significance of the chemical interaction of various components on LDH laminates and aims to effectively design more LDH-based cathodes for CIBs, which can even be extended to other halide-ion batteries like fluoride ion batteries and bromide ion batteries.
RESUMO
Transition-metal compounds (oxides, sulfides, hydroxides, etc.) as lithium-ion battery (LIB) anodes usually show extraordinary capacity larger than the theoretical value due to the transformation of LiOH into Li2O/LiH. However, there has rarely been a report relaying the transformation of LiOH into Li2O/LiH as the main reaction for LIBs, due to the strong alkalinity of LiOH leading to battery deterioration. In this work, layered silicate MgAl saponite (MA-SAP) is applied as a -OH donor to generate LiOH as the anode material of LIBs for the first time. The MA-SAP maintains a layered structure during the (dis)charging process and has zero-strain characteristic on the (001) crystal plane. In the discharging process, Mg, Al, and Si in the saponite sheets become electron-rich, while the active hydroxyl groups escape from the sheets and combine with lithium ions to form LiOH in the "caves" on sheets, and the LiOH continues to decompose into Li2O and LiH. Consequently, the MA-SAP delivers a maximum capacity of 536 mA h·g-1 at 200 mA·g-1 with a good high-current discharging ability of 155 mA h·g-1 after 1000 cycles under 1 A·g-1. Considering its extremely low cost and completely nontoxic characteristics, MA-SAP has great application prospects in energy storage. In addition, this work has an enlightening effect on the development of new anodes based on extraordinary mechanisms.
RESUMO
A fluoride-ion battery (FIB) is a novel type of energy storage system that has a higher volumetric energy density and low cost. However, the high working temperature (>150 °C) and unsatisfactory cycling performance of cathode materials are not favorable for their practical application. Herein, fluoride ion-intercalated CoFe layered double hydroxide (LDH) (CoFe-F LDH) was prepared by a facile co-precipitation approach combined with ion-exchange. The CoFe-F LDH shows a reversible capacity of â¼50 mAh g-1 after 100 cycles at room temperature. Although there is still a big gap between FIBs and lithium-ion batteries, the CoFe-F LDH is superior to most cathode materials for FIBs. Another important advantage of CoFe-F LDH FIBs is that they can work at room temperature, which has been rarely achieved in previous reports. The superior performance stems from the unique topochemical transformation property and small volume change (â¼0.82%) of LDH in electrochemical cycles. Such a tiny volume change makes LDH a zero-strain cathode material for FIBs. The 2D diffusion pathways and weak interaction between fluoride ions and host layers facilitate the de/intercalation of fluoride ions, accompanied by the chemical state changes of Co2+/Co3+ and Fe2+/Fe3+ couples. First-principles calculations also reveal a low F- diffusion barrier during the cyclic process. These findings expand the application field of LDH materials and propose a novel avenue for the designs of cathode materials toward room-temperature FIBs.