RESUMO
Constructing stable electrode/electrolyte interphase with fast interfacial kinetics is vital for fast-charging batteries. Herein, we investigate the interphase that forms between a high-voltage Na3 V2 (PO4 )2 F3 cathode and the electrolytes consisting of 3.0, 1.0, or 0.3â M NaClO4 in an organic carbonate solvent (47.5 : 47.5 : 5 mixture of EC: PC: FEC) during charging up to 4.5â V at 55 °C. It is found that a higher anion/solvent ratio in electrolyte solvation structure induces anion-dominated interphase containing more inorganic species and more anion derivatives (Cx ClOy ), which leads to a larger interfacial Na+ transport resistance and more unfavorable gas evolution. In comparison, a low anion/solvent ratio derives stable anion-tuned interphase that enables better interfacial kinetics and cycle ability. Importantly, the performance of a failed cathode is restored by triggering the decomposition of Cx ClOy species. This work elucidates the role of tuning interphase in fast-charging batteries.
RESUMO
It is challenging for flexible solid-state hybrid capacitors to achieve high-energy-high-power densities in both Li-ion and Na-ion systems, and the kinetics discrepancy between the sluggish faradaic anode and the rapid capacitive cathode is the most critical issue needs to be addressed. To improve Li-ion/Na-ion diffusion kinetics, flexible oxygen-deficient TiO2-x /CNT composite film with ultrafast electron/ion transport network is constructed as self-supported and light-weight anode for a quasi-solid-state hybrid capacitor. It is found that the designed porous yolk-shell structure endows large surface area and provides short diffusion length, the oxygen-deficient composite film can improve electrical conductivity, and enhance ion diffusion kinetic by introducing intercalation pseudocapacitance, therefore resulting in advance electrochemical properties. It exhibits high capacity, excellent rate performance, and long cycle life when utilized as self-supported anodes for Li-ion and Na-ion batteries. When assembled with activated carbon/carbon nanotube (AC/CNT) flexible cathode, using ion conducting gel polymer as the electrolyte, high energy densities of 104 and 109 Wh kg-1 are achieved at 250 W kg-1 in quasi-solid-state Li-ion and Na-ion capacitors (LICs and SICs), respectively. Still, energy densities of 32 and 36 Wh kg-1 can be maintained at high power densities of 5000 W kg-1 in LICs and SICs.
RESUMO
Lithium ion capacitors (LICs) are a new generation of energy storage devices that combine the super energy storage capability of lithium ion batteries with the satisfactory power density of supercapacitors. The development of high-performance LICs still faces great challenges due to the unbalanced reaction kinetics at the anode and cathode. Therefore, it is an inevitable need to enhance the electron/ion transfer capability of the anode materials. In this paper, to obtain a superior-rate and high-capacity Ni3S2-based anode, highly conductive Ti3C2Tx MXene sheets were introduced to sever as the carrier of Ni3S2 nanoparticles and simultaneously an amorphous carbon layer which coats onto the surface of Ni3S2 nanoparticles was in-situ generated by the carbonization of dopamine reactant. The as-synthesized Ni3S2/Ti3C2Tx/C composite exhibits a high specific surface area (112.6 m2/g) because of the addition of Ti3C2Tx that can reduce the aggregation of Ni3S2 nanoparticles and the in-situ generated amorphous carbon layer that can suppress the growth of Ni3S2 nanoparticles. The Ni3S2/Ti3C2Tx/C anode possesses a remarkable reversible discharge specific capacity (626.0 mAh/g under 0.2 A/g current density), which increases to 1150.8 mAh/g after 400-cycle charge/discharge measurement at the same measurement condition indicating eminent cyclability, along with superior rate capability. To construct a superior-performance LIC device, a sterculiae lychnophorae derived porous carbon (SLPC) cathode with an average discharge specific capacity of 73.4 mAh/g@0.1A/g was prepared. The Ni3S2/Ti3C2Tx/C//SLPC LIC device with optimal cathode/anode mass ratio has a satisfactory energy density ranging from 32.8 to 119.1 Wh kg-1 at the corresponding power density of 8799.4 to 157.5 W kg-1, together with a prominent capacity retention (95.5 %@1 A/g after 10,000 cycles).
RESUMO
In layered Li-rich materials, over stoichiometric Li forms an ordered occupation of LiTM6 in transition metal (TM) layer, showing a honeycomb superstructure along [001] direction. At the atomic scale, the instability of the superstructure at high voltage is the root cause of problems such as capacity/voltage decay of Li-rich materials. Here a Li-rich material with a high Li/Ni disorder is reported, these interlayer Ni atoms locate above the honeycomb superstructure and share adjacent O coordination with honeycomb TM. These NiâO bonds act as cable-stayed bridge to the honeycomb plane, and improve the high-voltage stability. The cable-stayed honeycomb superstructure is confirmed by in situ X-ray diffraction to have a unique cell evolution mechanism that it can alleviate interlaminar lattice strain by promoting in-plane expansion along a-axis and inhibiting c-axis stretching. Electrochemical tests also demonstrate significantly improved long cycle performance after 500 cycles (86% for Li-rich/Li half cell and 82% for Li-rich/Si-C full cell) and reduced irreversible oxygen release. This work proves the feasibility of achieving outstanding stability of lithium-rich materials through superstructure regulation and provides new insights for the development of the next-generation high-energy-density cathodes.
RESUMO
In commercial Li-ion batteries, the internal short circuits or over-lithiation often cause structural transformation in electrodes and may lead to safety risks. Herein, we investigate the over-discharged mechanism of LiCoO2/graphite pouch cells, especially spatially resolving the morphological, surface phase, and local electronic structure of LiCoO2 electrode. With synchrotron-based X-ray techniques and Raman mapping, together with spectroscopy simulations, we demonstrate that over-lithiation reaction is a surface effect, accompanied by Co reduction and surface structure transformation to Li2CoO2/Co3O4/CoO/Li2O-like phases. This surface chemical distribution variation is relevant to the depth and exposed crystalline planes of LiCoO2 particles, and the distribution of binder/conductive additives. Theoretical calculations confirm that Li2CoO2-phase has lower electronic/ionic conductivity than LiCoO2-phase, further revealing the critical effect of distribution of conductive additives on the surface chemical heterogeneity evolution. Our findings on such surface phenomena are non-trivial and highlight the capability of synchrotron-based X-ray techniques for studying the spatial chemical phase heterogeneity.
RESUMO
Potassium-ion capacitors (KICs) have received a surge of interest because of their higher reserves and lower costs of potassium than lithium. However, the cycle performance and capacity of potassium devices have been reported to be unsatisfactory. Herein, a unique crystalline MnCo2O4.5 and amorphous MnCo2S4 core/shell nanoscale flower structure grown on graphene (MCO@MCS@rGO) was synthesized by a two-step hydrothermal process and demonstrated in KICs. The MCO@MCS@rGO exhibits improved electrical conductivity and excellent structural integrity during the charging and discharging process. The reasons could be attributed to the cavity structure of MCO, the mechanical buffer and high electrolyte diffusion rate of MCS, and the auxiliary effect of graphene. The electrical conductivity of MCO@MCS shows a specific capacity of 272.3 mA h g-1 after 400 cycles at 1 A g-1 and a capacity of 125.6 mA h g-1 at 2 A g-1. Besides, the MCO@MCS@rGO and high-surface-area activated carbon in KICs exhibit a relative energy density of 85.3 W h kg-1 and a power density of 9000 W kg-1 and outstanding cycling stability with a capacity retention of 76.6% after 5000 cycles. Moreover, the reaction mechanism of MCO@MCS@rGO in the K-ion cell was investigated systematically using X-ray diffraction and transmission electron microscopy, providing guidance on the further development of pseudocapacitive materials.
RESUMO
Sluggish kinetics and limited reversible capacity present two major challenges for layered titanates to achieve satisfactory sodium-ion storage performance at subzero-temperatures (subzero-T). To facilitate sodiation dynamics and improve reversible capacity, we proposed an additive-free anode with Sn(II) located between layers. Sn-5s in interlayer-confining Sn(II), which has a larger negative charge, will hybridize with O-2p to trigger charge redistribution, thereby enhancing electronic conductivity. H-titanates with an open framework are designed to stabilize Sn(II) and restrain subsequent volume expansion, which could potentially surpass the capacity limitation of titanate-based materials via a joint alloying-intercalation reaction with high reversibility. Moreover, the generation of conductive Na14Sn4 and the expansion of interlayer spacing resulting from the interlayered alloying reaction are beneficial for charge transfer. These effects synergistically endow the modified sample with a considerably lower activation energy and a 3-fold increase in diffusion. Consequently, the designed anode delivers excellent subzero-T adaptability when compared to the unmodified sample, maintaining capacity retention of 91% after 1200 cycles at -20 °C and 90% after 850 cycles at -30 °C.