RESUMO
Anatase TiO2 as sodium-ion-battery anode has attracted increased attention because of its low volume change and good safety. However, low capacity and poor rate performance caused by low electrical conductivity and slow ion diffusion greatly impede its practical applications. Here, a bi-solvent enhanced pressure strategy that induces defects (oxygen vacancies) into TiO2 via N doping and reduces its size by using mutual-solvent ethanol and dopant dimethylformamide as pressure-increased reagent of tetrabutyl orthotitanate tetramer is proposed to fabricate N-doped TiO2/C nanocomposites. The induced defects can increase ion storage sites, improve electrical conductivity, and decrease bandgap and ion diffuse energy barrier of TiO2. The size reduction increases contact interfaces between TiO2 and C and shortens ion diffuse distance, thus increasing extra ion storage sites and boosting ion diffusion rate of TiO2. The N-doped TiO2 possesses highly stable crystal structure with a slightly increase of 0.86% in crystal lattice spacing and 3.2% in particle size after fully sodiation. Consequently, as a sodium-ion battery anode, the nanocomposite delivers high capacity and superior rate capability along with ultralong cycling life. This work proposes a novel pressure-induced synthesis strategy that provides unique guidance for designing TiO2-based anode materials with high capacity and excellent fast-charging capability.
RESUMO
Ni-rich layered oxides are promising lithium-ion batteries (LIBs) cathode materials for their high reversible capacity, but they suffer from fast structural degradation during cycling. Here, we report the Ce/Gd incorporated single-crystalline LiNi0.83 Co0.07 Mn0.10 O2 (SC-NCM) cathode materials with significantly enhanced cycling stability. The Gd ions are adequately incorporated in SC-NCM while Ce ions are prone to aggregate in the outer surface, resulting in the formation of a high-entropy zone in the near-surface of SC-NCM, including a Gd doped LiCeO2 (LCGO) shell and Ce/Gd dopant-concentrated layer. The high-entropy zone can effectively inhibit the oxygen evolution and prevent the formation of oxygen vacancies. Meanwhile, it leads to a greatly improved H2-H3 phase transformation reversibility and mitigated stress/strain caused by Li-ion extraction/insertion during (de)lithiation process. The synergetic effects of reduced oxygen vacancies concentration and mitigated stress/strain can effectively prevent the in-plane migration of TM ions, lattice planar gliding as well as the formation of intragranular nanocracks. Consequently, Ce/Gd incorporated SC-NCM (SC-NCM@CG2) delivers a high initial discharge specific capacity of 219.7â mAh g-1 at 0.1â C and an excellent cycling stability with a capacity retention of 90.2 % after 100â cycles at 1.0â C.
RESUMO
High-capacity Ni-rich layered oxides are promising cathode materials for fabrication of lithium-ion batteries (LIBs) with high energy density. However, thermal runaway of LIBs with these cathodes leads to great safety concerns. In this study, single crystalline LiNi0.9Co0.05Mn0.05O2 (NCM-SC) has been prepared and a flexible optical fiber was buried inside the pouch-type LIBs with NCM-SC cathode to in situ study its real-time temperature evolution during charge/discharge process. NCM-SC exhibits an enhanced Li+ ions transportation efficiency and electrode reaction kinetics, which can effectively reduce the generation of polarization heat and mitigate the internal temperature rise of the pouch-type battery. Meanwhile, solid-electrolyte interface (SEI) film decomposition and gas accumulation are effectively alleviated, due to the enhanced thermal stability of SEI film formed on NCM-SC. Moreover, the single crystal architecture can effectively retard layered to spinal and rock-salt phase transition, mitigate the crack formation and structural collapse. Consequently, NCM-SC exhibits an excellent electrochemical performance and enhanced thermal stability.
RESUMO
The pursuit of advanced materials to meet the escalating demands of energy storage system has led to the emergence of vertical graphene (VG) as a highly promising candidate. With its remarkable strength, stability, and conductivity, VG has gained significant attention for its potential to revolutionize energy storage technologies. This comprehensive review delves deeply into the synthesis methods, structural modifications, and multifaceted applications of VG in the context of lithium-ion batteries, silicon-based lithium batteries, lithium-sulfur batteries, sodium-ion batteries, potassium-ion batteries, aqueous zinc batteries, and supercapacitors. The review elucidates the intricate growth process of VG and underscores the paramount importance of optimizing process parameters to tailor VG for specific applications. Subsequently, the pivotal role of VG in enhancing the performance of various energy storage and conversion systems is exhaustively discussed. Moreover, it delves into structural improvement, performance tuning, and mechanism analysis of VG composite materials in diverse energy storage systems. In summary, this review provides a comprehensive look at VG synthesis, modification, and its wide range of applications in energy storage. It emphasizes the potential of VG in addressing critical challenges and advancing sustainable, high-performance energy storage devices, providing valuable guidance for the development of future technologies.
RESUMO
Zinc metal is an attractive anode material for rechargeable aqueous Zn-ion batteries (ZIBs). However, the dendrite growth, water-induced parasitic reactions, and freezing problem of aqueous electrolyte at low temperatures are the major roadblocks that hinder the widely commercialization of ZIBs. Herein, tetrahydrofuran (THF) is proposed as the electrolyte additive to improve the reversibility and stability of Zn anode. Theoretical calculation and experimental results reveal that the introduction of THF into the aqueous electrolyte can optimize the solvation structure which can effectively alleviate the H2O-induced side reactions and protect the Zn anode from corrosion. Moreover, THF can act as a hydrogen bond acceptor to interact with H2O, which can greatly reduce the activity of free H2O in electrolytes and improve the low-temperature electrochemical performance of Zn anode. As a result, the Zn anodes demonstrate high cyclic stability for 2800 h at 27 °C and over 4000 h at -10 °C at 1.0 mA cm-2 /1.0 mAh cm-2. The full cell exhibits excellent cyclic stability and rate capability at 27 and -10 °C. This work is expected to provide a new approach to regulate the aqueous electrolyte and Zn anode interface chemistry for highly stable and reversible Zn anodes.
RESUMO
Rapid capacity fading, interfacial instability, and thermal runaway due to oxygen loss are critical obstacles hindering the practical application and commercialization of Ni-rich cathodes (LiNi0.8Co0.1Mn0.1O2, NCM811). Herein, a Sn4+/F- codoping and LiF-coated Ni-rich cathode, denoted as NCM811-SF, is structurally fabricated that demonstrates very high cyclic and thermal stabilities. The introduction of Sn4+ regulates the local electronic structure and facilitates the conversion of the layered structure into a spinel phase; F- captures lithium impurities to form LiF coatings and forms TM-F bonds to reduce Ni/Li disordering. The compositionally complex codoping strategy reduces the internal structure strain, inhibits the Li+/Ni2+ intermixing during cycling and degradation of the nanoscale structure, and further improves the thermal stability and the crystal structure. The cathodic electrode showed a little volume shift at 2.8-4.5 V, which significantly decreased lattice flaws and fractures generated by local strain, based on detailed analyses performed using COMSOL simulations, X-ray diffraction, and scanning transmission electron microscopy. Benefiting from this, after 300 cycles, our as-prepared NCM811-SF cathode maintains 85.4% of its initial capacity at 4.5 V and has an excellent reversible capacity equal to 169 mAh·g-1 at 1 C. In addition, the NCM811-SF/graphite cell in a pouch-type complete cell retained 94.8% of its starting capacity following 500 cycles. These findings underscore the effectiveness of introducing the Sn-O and TM-F bonds in improving the durability and electrochemical efficiency of the cathode material, which makes it a good choice for high-efficiency Li-ion batteries.
RESUMO
The cycling stability of LiNi0.8Co0.1Mn0.1O2 under high voltages is hindered by the occurrence of hybrid anion- and cation-redox processes, leading to oxygen escape and uncontrolled phase collapse. In this study, an interfacial engineering strategy involving a straightforward mechanical ball milling and low-temperature calcination, employing a Se-doped and FeSe2&Fe2O3-modified approach is proposed to design a stable Ni-rich cathode. Se2- are selectively adsorbed within oxygen vacancies to form OâTMâSe bond, effectively stabilizing lattice oxygen, and preventing structural distortion. Simultaneously, the Se-NCM811//FeSe2//Fe2O3 self-assembled electric field is activated, improving interfacial charge transfer and coupling. Furthermore, FeSe2 accelerates Li+ diffusion and reacts with oxygen to form Fe2O3 and SeO2. The Fe2O3 coating mitigates hydrofluoric acid erosion and acts as an electrostatic shield layer, limiting the outward migration of oxygen anions. Impressively, the modified materials exhibit significantly improved electrochemical performance, with a capacity retention of 79.7% after 500 cycles at 1C under 4.5 V. Furthermore, it provides an extraordinary capacity retention of 94.6% in 3-4.25 V after 550 cycles in pouch-type full battery. This dual-modification approach demonstrates its feasibility and opens new perspective for the development of stable lithium-ion batteries operating at high voltages.
RESUMO
Improving the long-term cycling stability and energy density of all-solid-state lithium (Li)-metal batteries (ASSLMBs) at room temperature is a severe challenge because of the notorious solid-solid interfacial contact loss and sluggish ion transport. Solid electrolytes are generally studied as two-dimensional (2D) structures with planar interfaces, showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces. Herein, three-dimensional (3D) architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment. Multiple-type electrolyte films with vertical-aligned micro-pillar (p-3DSE) and spiral (s-3DSE) structures are rationally designed and developed, which can be employed for both Li metal anode and cathode in terms of accelerating the Li+ transport within electrodes and reinforcing the interfacial adhesion. The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm-2. The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm-2 (LFP) and 3.92 mAh cm-2 (NCM811). This unique design provides enhancements for both anode and cathode electrodes, thereby alleviating interfacial degradation induced by dendrite growth and contact loss. The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.
RESUMO
The development of highly efficient hydrogen evolution electrocatalysts with platinum-like activity requires precise control of active sites through interface engineering strategies. In this study, a heterostructured Co5.47N/Mo5N6 catalyst (CoMoNx) on carbon cloth (CC) was synthesized using a combination of dip-etching and vapor nitridation methods. The rough nanosheet surface of the catalyst with uniformly distributed elements exposes a large active surface area and provides abundant interface sites that serve as additional active sites. The CoMoNx was found to exhibit exceptional hydrogen evolution reaction (HER) activity with a low overpotential of 44 mV at 10 mA cm-2 and exceptional stability of 100 h in 1.0 M KOH. The CoMoNx(-)||RuO2(+) system requires only 1.81 V cell voltage to reach a current density of 200 mA cm-2, surpassing the majority of previously reported electrolyzers. Density functional theory (DFT) calculations reveal that the strong synergy between Co5.47N and Mo5N6 at the interface can significantly reduce the water dissociation energy barrier, thereby improving the kinetics of hydrogen evolution. Furthermore, the rough nanosheet architecture of the CoMoNx catalyst with abundant interstitial spaces and multi-channels enhances charge transport and reaction intermediate transportation, synergistically improving the performance of the HER for water splitting.
RESUMO
Pushing the limit of cutoff potentials allows nickel-rich layered oxides to provide greater energy density and specific capacity whereas reducing thermodynamic and kinetic stability. Herein, a one-step dual-modified method is proposed for in situ synthesizing thermodynamically stable LiF&FeF3 coating on LiNi0.8 Co0.1 Mn0.1 O2 surfaces by capturing lithium impurity on the surface to overcome the challenges suffered. The thermodynamically stabilized LiF&FeF3 coating can effectively suppress the nanoscale structural degradation and the intergranular cracks. Meanwhile, the LiF&FeF3 coating alleviates the outward migration of Oα- (α<2), increases oxygen vacancy formation energies, and accelerates interfacial Li+ diffusion. Benefited from these, the electrochemical performance of LiF&FeF3 modified materials is improved (83.1% capacity retention after 1000 cycles at 1C), even under exertive operational conditions of elevated temperature (91.3% capacity retention after 150 cycles at 1C). This work demonstrates that the dual-modified strategy can simultaneously address the problems of interfacial instability and bulk structural degradation and represents significant progress in developing high-performance lithium-ion batteries (LIBs).
RESUMO
Metallic zinc anodes of aqueous zinc ion batteries suffer from severe dendrite and side reaction issues, resulting in poor cycling stability, especially at high rates and capacities. Herein, we develop two three-dimensional hierarchical graphene matrices consisting of nitrogen-doped graphene nanofibers clusters anchored on vertical graphene arrays of modified multichannel carbon. The graphene matrix with radial direction carbon channels possesses high surface area and porosity, which effectively minimizes the surface local current density, manipulates the Zn2+ ions concentration gradient, and homogenizes the electric field distribution to regulate Zn deposition. As a result, the engineered matrices achieve a superior coulombic efficiency of 99.67% over 3000 cycles at 120 mA cm-2, the symmetric cells with the composite zinc anode demonstrates 2600 h dendrite-free cycles at 80 mA cm-2 and 80 mAh cm-2. The as-designed full cell exhibits an inspiring capacity of 16.91 mAh cm-2. The Zn capacitor matched with activated carbon shows a superior long-term cycle performance of 20000 cycles at 40 mA cm-2. This strategy of constructing a 3D hierarchical structure for Zn anodes may open up a new avenue for metal anodes operating under high rates and capacities.