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The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.
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Battery materials, which store energy by combining mechanisms of intercalation, conversion, and alloying, provide promisingly high energy density but usually suffer from fast capacity decay due to the drastic volume change upon cycling. Particularly, the significant volume shrinkage upon mass (Li+, Na+, etc.) extraction inevitably leads to the formation of pores in materials and their final pulverization after cycling. It is necessary to explore the failure mechanism of such battery materials from the microscopic level in order to understand the evolution of porous structures. Here, prototyped Sb2Se3 nanowires are targeted to understand the structural failures during repetitive (de)sodiation, which exhibits mainly alloying and conversion mechanisms. The fast growing nanosized pores embedded in the nanowire during desodiation are identified to be the key factor that weakens the mechanical strength of the material and thus cause a rapid capacity decrease. To suppress the pore development, we further limit the cutoff charge voltage in a half-cell against Na below a critical value where the conversion reaction of such a material system is yet happening, the result of which demonstrates significantly improved battery performance with well-maintained structural integrity. These findings may shed some light on electrode failure investigation and rational design of advanced electrode materials with long cycling life.
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Li- and Mn-rich (LMR) cathode materials have been considered as promising candidates for energy storage applications due to high energy density. However, these materials suffer from a serious problem of voltage fade. Oxygen loss and the layered-to-spinel phase transition are two major contributors of such voltage fade. In this paper, using a combination of X-ray diffraction (XRD), pair distribution function (PDF), X-ray absorption (XAS) techniques, and aberration-corrected scanning transmission electron microscopy (STEM), we studied the effects of micro structural defects, especially the grain boundaries, on the oxygen loss and layered-to-spinel phase transition through prelithiation of a model compound Li2Ru0.5Mn0.5O3. It is found that the nanosized micro structural defects, especially the large amount of grain boundaries created by the prelithiation can greatly accelerate the oxygen loss and voltage fade. Defects (such as nanosized grain boundaries) and oxygen release form a positive feedback loop, promote each other during cycling, and accelerate the two major voltage fade contributors: the transition metal reduction and layered-to-spinel phase transition. These results clearly demonstrate the important relationships among the oxygen loss, microstructural defects and voltage fade. The importance of maintaining good crystallinity and protecting the surface of LMR material are also suggested.
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Recharging primary batteries is of great importance for increasing the energy density of energy storage systems to power electric aircraft and beyond. Carbon fluoride (CFx) cathodes are characterized by high specific capacity and energy density (865 mAh g-1 and 2180 Wh kg-1, respectively). Preventing the crystallization of LiF with an intermediate and lowering the energy barrier from LiF to CFx is expected to render the Li/CFx battery reversible. In this study, taking the advantage of a high-voltage-stable all-fluorinated electrolyte containing the boron-based anion receptor tris(trimethylsilyl)borate (TMSB), a rechargeable Li/CFx battery was realized with a reversible capacity of 465.9 mAh g-1 and an energy density of 1183.9 Wh kg-1, approximately 53% of that in the first discharge. After the first discharge, the charge-discharge profile featured rechargeable characteristics. In situ X-ray diffraction, ex situ soft X-ray absorption spectroscopy, pair distribution function analysis, and other measurements confirmed the generation and decomposition of Li-F and C-F bonds during cycling. Density functional theory calculations and nuclear magnetic resonance spectroscopy confirmed that TMSB serves as an anion carrier through the generation of a [TMSB-F]- complex, facilitating the conversion reactions during cycling. This study demonstrated a facile and low-cost approach for realizing high-energy-density, reversible Li/CFx batteries.
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Ni-rich cathode materials suffer from rapid capacity fading caused by interface side reactions and bulk structure degradation. Previous studies show that Co is conducive to bulk structure stability and sulfate can react with the residual lithium (LiOH and Li2CO3) on the surface of Ni-rich cathode materials and form a uniform coating to suppress the side reactions between the cathode and electrolyte. Here, CoSO4 is utilized as a modifier for LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode materials. It reacts with the residual lithium on the surface of the NCM811 cathode to form Li-ion conductive Li2SO4 protective layers and Co doping simultaneously during the high-temperature sintering process, which can suppress the side reactions between the Ni-rich cathode and electrolyte and effectively prevent the structural transformation. As a result, the co-modified NCM811 cathode with 3 wt% CoSO4 exhibits an improved cycling performance of 81.1% capacity retention after 200 cycles at 1C and delivers an excellent rate performance at 5C of 187.4 mA h g-1, which is 10.2% higher than that of the pristine NCM811 cathode.
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Non-noble metal catalysts now play a key role in promoting efficiently and economically catalytic reduction of CO2 into clean energy, which is an important strategy to ameliorate global warming and resource shortage issues. Here, a non-noble bimetallic catalyst of CoFe/Fe3 O4 nanoparticles is successfully designed with a core-shell structure that is well dispersed on the defect-rich carbon substrate for the hydrogenation of CO2 under mild conditions. The catalysts exhibit a high CO2 conversion activity with the rate of 30% and CO selectivity of 99%, and extremely robust stability without performance decay over 90 h in the reverse water gas shift reaction process. Notably, it is found that the reversible exsolution/dissolution of cobalt in the Fe3 O4 shell will lead to a dynamic and reversible deactivation/regeneration of the catalysts, accompanying by shell thickness breathing during the repeated cycles, via atomic structure study of the catalysts at different reaction stages. Combined with density functional theory calculations, the catalytic activity reversible regeneration mechanism is proposed. This work reveals the structure-property relationship for rational structure design of the advanced non-noble metallic catalyst materials with much improved performance.
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Li- and Mn-rich cathodes (LMRs) with cationic and anionic redox reactions are considered as promising cathode materials for high-energy-density Li-ion batteries. However, the oxygen redox process leads to lattice oxygen loss and structure degradation, which would induce serious voltage fade and capacity loss and thus limit the practical application. High-valent and electrochemical inactive d0 element doping is an effective method to tune the crystal and electronic structures, which are the main factors for the electrochemical stability. Herein, noticeably inhibited oxygen loss, reduced voltage fade, enhanced rate performance, and improved structure stability and thermal stability of LMRs have been realized by Ti4+ and Zr4+ dual-doping. The underlying modulation mechanisms are unraveled by combining differential electrochemical mass spectrometry, soft X-ray absorption spectroscopies, in situ XRD measurements, etc. The dual-doping reduces the covalency of the TM-O bond, mitigates the irreversible oxygen release during the oxygen redox, and stabilizes the layered framework. The expanded lithium layer facilitates the lithium diffusion kinetics and structure stability. This study may result in the fundamental understanding of crystal and electronic structure evolution in LMRs and contribute to the development of high capacity cathodes.
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The LiCoO2 cathode undergoes undesirable electrochemical performance when cycled with a high cut-off voltage (≥4.5 V versus Li/Li+). The unstable interface with poor kinetics is one of the main contributors to the performance failure. Hence, a hybrid Li-ion conductor (Li1.5Al0.5Ge1.5P3O12) and electron conductor (Al-doped ZnO) coating layer was built on the LiCoO2 surface. Characterization studies prove that a thick and conductive layer is homogeneously covered on LiCoO2 particles. The coating layer can not only enhance the interfacial ionic and electronic transport kinetics but also act as a protective layer to suppress the side reactions between the cathode and electrolyte. The modified LiCoO2 (HC-LCO) achieves an excellent cycling stability (77.1% capacity retention after 350 cycles at 1C) and rate capability (139.8 mAh g-1 at 10C) at 3.0-4.6 V. Investigations show that the protective layer can inhibit the particle cracks and Co dissolution and stabilize the cathode electrolyte interface (CEI). Furthermore, the irreversible phase transformation is still observed on the HC-LCO surface, indicating the phase transformation of the LiCoO2 surface may not be the main factor for fast performance failure. This work provides new insight of interfacial design for cathodes operating with a high cut-off voltage.
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Ni-rich cathode materials LiNixCoyMn1-x-yO2 (x ≥ 0.6) have attracted much attention due to their high capacity and low cost. However, they usually suffer from rapid capacity decay and short cycle life due to their surface/interface instability, accompanied by the high Ni content. In this work, with the Ni0.9Co0.05Mn0.05(OH)2 precursor serving as a coating target, a Li-ion conductor Li2SiO3 layer was uniformly coated on Ni-rich cathode material LiNi0.9Co0.05Mn0.05O2 by a precoating and syn-lithiation method. The uniform Li2SiO3 coating layer not only improves the Li-ion diffusion kinetics of the electrode but also reduces mechanical microstrain and stabilizes the surface chemistry and structure with a strong Si-O covalent bond. These results will provide further in-depth understanding on the surface chemistry and structure stabilization mechanisms of Ni-rich cathode materials and help to develop high-capacity cathode materials for next-generation high-energy-density Li-ion batteries.
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Hard carbon materials are considered as the most promising anode for sodium-ion batteries (SIBs). However, the high cost and poor rate performance hinder their application in SIBs. Moreover, the controversial mechanism of Na-ion storage restricts the improvement of hard carbon anodes. Herein, hard carbon micro-nano tubes (HCMNTs) from low-cost biomass kapok fibers are prepared as a promising anode for SIBs. Benefitting from the micro-nano structure, which offers low surface area and short Na+ diffusion path, 1400HCMNT possesses a good initial Coulombic efficiency of 80%, a high reversible capacity of 290 mA h g-1, and an excellent rate capacity. Furthermore, electron paramagnetic resonance and thermogravimetric analysis were applied to investigate the Na-ion storage mechanism in the HCMNTs. Sodium is stored in the hard carbon in an ionic state in the slope region and as quasi-liquid metallic sodium clusters in the low-voltage plateau.
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Layered germanium phosphide (GeP), a recently developed two-dimensional material, promises highly attractive theoretical capacity for use as a lithium-ion battery anode. Here, we comprehensively investigate its electrochemical performance and the modification mechanism. GeP flakes demonstrate large initial discharge/charge capacity and high initial Coulombic efficiency. However, the cycling performance is disappointing in the potential window of 0.001-3 V in which capacity retention is only â¼18% after 100 cycles. In situ transmission electron microscopy reveals that the poor cycling behavior results in the unexpected large volume change induced by complex reaction processes in cycles. Serious cracking and fracture appear clearly on the electrode surface after cycling. Narrowing the working voltage window to 0.001-0.85 V, cycling stability will be greatly enhanced, with 75% capacity retaining after 100 cycles and â¼50% left after 350 cycles due to the absence of the dealloying of Li3P in the narrowed working voltage window. Additionally, the electric contact among the electrode components has been enhanced by the alleviation of the electrode volume change in the narrowed working voltage window. Our work provides one effective method to give a deep understanding of the high-energy-density electrode failure and helps to narrow the huge gap between the microstructure and the performance of the electrode.
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In this work, mesoporous hard carbon materials were synthesized and modified by compositing a carbon coating and carbon nanotubes (CNTs), reducing the surface area and improving the conductivities without changing the microstructures of the anodes, which enhances the coulombic efficiencies and rate performances of sodium-ion batteries (SIBs).
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A hexagonal FeSe nanoparticle anode with a novel reaction mechanism and mechanical stability may fully facilitate the desirable rate capability and cycling performance in sodium-ion batteries. In situ TEM reveals that hexagonal FeSe nanoparticle transition to the Fe and Na2Se phase during sodiation, while the products transform to the tetragonal FeSe phase after desodiation.
Asunto(s)
Nanopartículas/química , Sodio/química , Espectroscopía Dieléctrica , Conductividad Eléctrica , Suministros de Energía Eléctrica , Hierro/química , Selenio/químicaRESUMEN
Although various cathode materials have been explored to improve the energy density of lithium-ion batteries, LiCoO2 is still the first choice for 3C consumer electronics due to the high tap density and high volumetric energy density. However, only 0.5 mol of lithium ions can be extracted from LiCoO2 to avoid side reactions and irreversible structure change, which typically occur at high voltage (>4.2 V). To improve the electrochemical performances of the LiCoO2 cathode material at high cut-off voltage and elevated temperature for higher energy density, an in situ formed spinel interfacial coating layer of LiCo xMn2- xO4 is achieved by the reaction of the surface region of the LiCoO2 host. The capacity retention of the modified LiCoO2 cycled at a high voltage of 4.5 V is significantly increased from 15.5 to 82.0% after 300 cycles at room temperature, due to the stable spinel interfacial inhibiting interfacial reactions between LiCoO2 and the electrolyte as confirmed by impedance spectroscopy. We further demonstrated that LiCoO2 with the spinel interfacial layer also exhibits an excellent cycling stability at a high temperature of 45 °C.
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Na3[Ti2P2O10F] was synthesized by a hydrothermal method. It has an open framework structure consisting of TiFO5 octahedra and PO4 tetrahedra. The feasibility of Na3[Ti2P2O10F] as an anode material for lithium-ion batteries was first studied. Na3[Ti2P2O10F] exhibits a reversible capacity of more than 200 mAh g(-1) at a discharge/charge current rate of 20 mA g(-1) (â¼0.1 C) and 105 mA g(-1) at a discharge/charge current rate of 400 mA g(-1) (â¼2 C) with a lower intercalation voltage. The result of in situ X-ray diffraction test shows the structural evolution during the first discharge/charge cycle. The structure of Na3[Ti2P2O10F] was kept during discharge/charge with a slight change of the lattice parameters, which indicates a lithium solid solution behavior.
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Carbon-coated Li2MoO4 hexagonal hollow nanotubes were fabricated via a facile sol-gel method involving the solution synthesis of Li2MoO4 with subsequent annealing under an inert atmosphere to decompose the organic carbon source. To the best of our knowledge, this is the first report on the synthesis of Li2MoO4 nanotubes. More significantly, we have found that Li2MoO4 can be used as an anode material for lithium-ion batteries (LIBs). When evaluated as an anode material, the carbon-coated Li2MoO4 hollow nanotubes show an excellent electrochemical performance with a high reversible capacity (â¼550 mA h g(-1)) after 23 cycles, good rate capability and cycling stability. Meanwhile, carbon-free Li2MoO4 sample, fabricated via a solid state reaction, was also prepared for comparison. The Li storage mechanism has been investigated in-detail by advanced XPS, in situ XRD and HRTEM.