RESUMO
Solid-electrolyte interphase (SEI) seriously affects battery's cycling life, especially for high-capacity anode due to excessive electrolyte decomposition from particle fracture. Herein, we report an ultrathin SEI (3-4â nm) induced by Cu+ -tailored double electrical layer (EDL) to suppress electrolyte consumption and enhance cycling stability of CuS anode in sodium-ion batteries. Unique EDL with SO3 CF3 -Cu complex absorbing on CuS in NaSO3 CF3 /diglyme electrolyte is demonstrated by in situ surface-enhanced Raman, Cyro-TEM and theoretical calculation, in which SO3 CF3 -Cu could be reduced to CuF2 -rich SEI. Dispersed CuF2 and F-containing compound can provide good interfacial contact for formation of ultrathin and stable SEI film to minimize electrolyte consumption and reduce activation energy of Na+ transport. As a result, the modified CuS delivers high capacity of 402.8â mAh g-1 after 7000â cycles without capacity decay. The insights of SEI construction pave a way for high-stability electrode.
RESUMO
FeP has emerged as an appealing anode material for lithium-ion batteries (LIBs) thanks to its high theoretical capacity, safe voltage platform and rich resources. Nevertheless, sluggish charge transfer kinetics, inevitable volume expansion and easy agglomeration of active materials limit its practical applications. Here, novel Cu-doped FeP@C was synthesized by a synergistic strategy of metal doping and in situ carbon encapsulation. The optimized Cu-doped FeP@C anode demonstrates a highly reversible specific capacity (920 mAh g-1 at 0.05 A g-1), superb rate performance (345 mAh g-1 at 5 A g-1) and long-term cycle stability (340 mAh g-1 at 2 A g-1 after 600 cycles). The electrochemical mechanism was investigated by cyclic voltammetry, kinetic analysis and DFT calculations. The results reveal that carbon frameworks can improve the conductivity and slow down the volume expansion, with highly dispersed FeP facilitating Li-ion migration during the charge and discharge processes. Additionally, Cu doping leads to rearrangement of the charge density and an additional lattice distortion in FeP, which boosts the electron mobility and enriches the surface-active sites, promoting electrochemical reaction and charge storage. This study presents a feasible and effective design for developing transition metal phosphate (TMP) anodes for high-performance LIBs.
RESUMO
Increasing insertion host materials are developed as high-performance anodes of "rocking-chair" zinc ion batteries. However, most of them show unsatisfactory rate capabilities. Herein, layered BiOIO3 is reported as an excellent insertion host and a zinc ion conductor, i.e., Zn3(PO4)2·4H2O (ZPO), is introduced to construct a BiOIO3@ZPO heterojunction with a built-in electric field (BEF). Both ZPO and a BEF obviously enhance Zn2+ transfer and storage, which is proven by theoretical calculations and experimental studies. The conversion-type mechanism of BiOIO3 is revealed through ex situ characterizations. The optimized electrode exhibits a high reversible capacity of 130 mAh g-1 at 0.1 A g-1, a low average discharge voltage of 0.58 V, an ultrahigh rate performance with 68 mAh g-1 at 5 A g-1 (52% of capacity at 0.1 A g-1), and an ultralong cyclic life of 6000 cycles at 5 A g-1. Significantly, the BiOIO3@ZPO//Mn3O4 full cell shows a good cyclic life of 67 mAh g-1 over 1000 cycles at 0.1 A g-1. This work provides a new insight into the design of anodes with excellent rate capability.
RESUMO
Nano-sized two-dimensional carbonaceous materials have been widely used as the matrix for alloying-type and conversion-type anode materials for Li-ion batteries (LIBs) to improve structural stability and rate performance. However, relevant synthesis usually requires rigorous conditions and chronic reaction processes. Herein, we have designed a simple solvothermal reaction and heat treatment to prepare a novel CoO/Co/C two-dimensional nanosheet (CoO/Co/C 2DNS) by adopting cellulose nanofibers (CNFs) as the precursor. The unique characteristics of CNFs facilitate the uniform distribution of active materials on the surface and the construction of two-dimensional nanostructure via self-assembly. It is worth noting that CoO/Co/C 2DNS exhibits a striking synergistic effect since the porous 2D carbon framework offers additional pseudo-capacitance and enhances the electronic conductivity, while the ultrafine active materials encapsulated inside shorten the Li-ions diffusion pathways and relieve the volume change. Benefit from the unique structure, the composite anode delivered outstanding rate performance (â¼500 mAh g-1 at 10 A g-1) and superior long-range cycling performance up to 800 cycles even at 2 A g-1. This work provides a new strategy for the synthesis of nano-sized 2D composite, offering a promising route to construct high performance conversion-type anodes for next-generation LIBs.
Assuntos
Lítio , Nanofibras , Celulose , Fontes de Energia Elétrica , EletrodosRESUMO
Transition metal dichalcogenides are regarded as promising anode materials for potassium-ion batteries (PIBs) because of their high theoretical capacities. However, due to the large atomic radius of K+, the structural damage caused by the huge volume expansion upon potassiation is much more severe than that of their lithium counterparts. In this research, a stress-dispersed structure with Co3Se4 nanocrystallites orderly anchored on graphene sheets is achieved through a two-step hydrothermal treatment to alleviate the structural deterioration. The ability to reduce the contact stress by the well-dispersed Co3Se4 nanocrystallites during K+ intercalation, together with the highly conductive graphene matrix, provides a more reliable and efficient anode architecture than its two agminated counterparts. Given these advantages, the optimized electrode delivers excellent cycling stability (301.8 mA h g-1 after 500 cycles at 1 A g-1), as well as an outstanding rate capacity (203.8 mA h g-1 at 5 A g-1). Further in situ and ex situ characterizations and density functional theory calculations elucidate the potassium storage mechanism of Co3Se4 during the conversion reaction and reveal the fast electrochemical kinetics of the rationally designed electrode. This work provides a practical approach for constructing stable metal-selenide anodes with long cycle life and high-rate performance for PIBs.
RESUMO
Batteries capable of quick charging as fast as fossil fuel vehicles are becoming a vital issue in the electric vehicle market. However, conversion-type materials promising as a next-generation anode have many problems to satisfy fast charging and long-term cycles due to their low conductivity and large irreversibility despite a high theoretical capacity. Here, we report effective strategies for a SnO2-based anode to enable rapid-charging, long-cycle, and high reversible capacity. The quantum size of SnO2 nanoparticles uniformly embedded within a 3D conductive carbon matrix as a prerequisite for high reversible capacity increases the interdiffusion layer and facilitates a highly reversible conversion reaction between Li2O/Sn and SnO2. In particular, the Sn-C chemical bond achieves ion-site control and direct electron transfer, enabling boost charging. Further, the robust and porous structure of the binder-free three-dimensional electrode buffers the massive volume expansion during Li insertion/desertion and allows for multidimensional rapid-ion diffusion. As a result, our quantum SnO2 anode delivers a high reversible capacity of about 753 mAh g-1 with a 468% capacity increase after 4000 cycles at 10 C. It also presents a gradually increasing capacity up to 548 mAh g-1 even at 20 C and superior cyclability over 20â¯000 cycles in capacity stabilization. This study will contribute to designing aerofilm-based conversion-type electrodes for fast charging devices.
RESUMO
High-entropy oxides (HEOs), which are a new class of single-phase solid solution materials, have recently attracted significant attention as an anode material for lithium-ion batteries (LIBs). In this study, (MgCoNiZn)1-xLixO (x = 0.05, 0.15, 0.25, and 0.35) HEOs were synthesized and their electrochemical performances as the anode material were observed in LIBs. X-ray photoelectron spectroscopy (XPS) analysis showed that the increase in the lithium cation concentration causes generation of more oxygen vacancies, which greatly affected the electrochemical performance of (MgCoNiZn)1-xLixO HEO anodes, in the structure. The more the oxygen vacancy concentration in the anode, the higher the discharge capacity in the LIB. The (MgCoNiZn)0.65Li0.35O anode had 1930 mA h g-1 initial and 610 mA h g-1 stable (after 130 cycles) discharge capacities at a current density of 1000 mA g-1. This work clearly indicated that designing a HEO with abundant oxygen vacancies in the structure was a very efficient strategy to improve the electrochemical performance of the HEO electrode for LIBs.
RESUMO
The carbon coating strategy is intensively used in the modification of conversion-type anode materials to improve their cycling stability and rate capability. Thus, it is necessary to elucidate the modification mechanism induced by carbon coating. For this purpose, bare ZnMn2O4, carbon-derivative-coated ZnMn2O4, and carbon-coated ZnO-MnO composite materials have been synthesized and investigated in-depth. Herein, high-temperature synchrotron radiation diffraction is used to monitor the phase transition from ZnMn2O4 to ZnO-MnO composite during the carbonization process. The electrochemical performance has been evaluated by cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The carbon- and carbon-derivative-coated samples display well-improved cycling stability in terms of suppressed electrode polarization, a moderate increase in resistance, and slight capacity variation. The influence of carbon coating on the intrinsic conversion process is investigated by ex situ X-ray absorption spectroscopy, which reveals the evolution of Zn and Mn oxidation states. This result confirms that the strong capacity variation of the bare ZnMn2O4 is induced not only by the reversible charge storage in the solid electrolyte interphase but also by the phase evolution of active materials. Carbon coating is an effective method to prevent the additional oxidation of MnO to Mn3O4, which leads to a stabilization of the main conversion reaction.
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The initial reversible capacity, a critical impediment in transition metal oxide-based anodes, is augmented in conversion-reaction-involved CoO anodes for lithium-ion batteries, by incorporating a chemically synthesized Ag nanophase. With an increase in the added amount of Ag nanophase from 5 to 15 wt %, the initial capacity loss decreases linearly up to 31.7%. The Ag nanophase maintains its pristine metallic nature without undergoing phase transformations, even during repeated vigorous electrochemical reactions of the active CoO phase. Complementary ex situ chemical/physical analyses suggest that the Ag nanophase promotes the catalytic generation of reversible gel-like/polymeric films wherein lithium ions are stored capacitively in the low-voltage region below 0.7 V during discharging. These scientific findings would provide a heretofore unrecognized pathway to resolving a major issue associated with the critical irreversibility in conversion-type transition metal oxide anodes.
RESUMO
A high-performance α-MoO3/multiwalled carbon nanotube (MWCNT) nanocomposite material is synthesized via a novel surfactant-assisted solvothermal process followed by low-temperature calcination. Its structure, composition, and morphology are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, carbon element analysis, nitrogen adsorption-desorption determination, scanning electron microscopy, and transmission electron microscopy techniques. Its electrochemical performance as a high-capacity lithium-ion-battery anode material is investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic discharge/recharge methods. This composite material exhibits not only high capacity but also excellent rate capability and cyclability. For example, when the discharge/charge current density is increased from 0.1 to 2 A g(-1), the reversible charge capacity is only decreased from 1138.3 to 941.4 mAh g(-1), giving a capacity retention of 82.7%. Even if it is cycled at a high current density of 20 A g(-1), a reversible charge capacity of 490.2 mAh g(-1) is still retained, showing a capacity retention of 43.1%. When it is repeatedly cycled at a current of 0.5 A g(-1), the initial reversible charge capacity is 1041.1 mAh g(-1). A maximum charge capacity of 1392.2 mAh g(-1) is achieved at the 292th cycle. After 300 cycles, a high charge capacity of 1350.3 mAh g(-1) is maintained. Enhancement of the electrical conduction contributed by the MWCNT composite component as well as the loose and porous texture of the MoO3/MWCNT composite is suggested to be responsible for the excellent performance.