RESUMO
Two different types of electrolytes (co-solvent and multi-salt) are tested for use in high voltage LiNi0.5Mn1.5O4||Si/graphite full cells and compared against a carbonate-based standard LiPF6 containing electrolyte (baseline). Ex situ postmortem XPS analysis on both anodes and cathodes over the life span of the cells reveals a continuously growing SEI and CEI for the baseline electrolyte. The cells cycled in the co-solvent electrolyte exhibited a relatively thick and long-term stable CEI (on LNMO), while a slowly growing SEI was determined to form on the Si/graphite. The multi-salt electrolyte offers more inorganic-rich SEI/CEI while also forming the thinnest SEI/CEI observed in this study. Cross-talk is identified in the baseline electrolyte cell, where Si is detected on the cathode, and Mn is detected on the anode. Both the multi-salt and co-solvent electrolytes are observed to substantially reduce this cross-talk, where the co-solvent is found to be the most effective. In addition, Al corrosion is detected for the multi-salt electrolyte mainly at its end-of-life stage, where Al can be found on both the anode and cathode. Although the co-solvent electrolyte offers superior interface properties in terms of the limitation of cross-talk, the multi-salt electrolyte offers the best overall performance, suggesting that interface thickness plays a superior role compared to cross-talk. Together with their electrochemical cycling performance, the results suggest that multi-salt electrolyte provides a better long-term passivation of the electrodes for high-voltage cells.
RESUMO
Functional polymers can be used as electrolyte and binder materials in solid-state batteries. This often requires performance targets in terms of both the transport and mechanical properties. In this work, a model ionic conductive polymer system, i.e., poly(ethylene oxide)-LiTFSI, was used to study the impact of salt concentrations on mechanical properties, including different types of elastic moduli and the viscoelasticity with both nonequilibrium and equilibrium molecular dynamics simulations. We found an encouragingly good agreement between experiments and simulations regarding Young's modulus, bulk modulus, and viscosity. In addition, we identified an intermediate salt concentration at which the system shows high ionic conductivity, high Young's modulus, and short elastic restoration time. Therefore, this study laid the groundwork for investigating ionic conductive polymer binders with self-healing functionality from molecular dynamics simulations.
RESUMO
Aqueous lithium-ion batteries (ALIBs) are promising for large-scale energy storage systems because of the cost-effective, intrinsically safe, and environmentally friendly properties of aqueous electrolytes. Practical application is however impeded by interfacial side-reactions and the narrow electrochemical stability window (ESW) of aqueous electrolytes. Even though higher electrolyte salt concentrations (e.g., water-in-salt electrolyte) enhance performance by widening the ESW, the nature and extent of side-reaction processes are debated and more fundamental understanding thereof is needed. Herein, the interfacial chemistry of one of the most popular electrode materials, V2O5, for aqueous batteries is systematically explored by a unique set of operando analytical techniques. By monitoring electrode/electrolyte interphase deposition, electrolyte pH, and gas evolution, the highly dynamic formation/dissolution of V2O5/V2O4, Li2CO3 and LiF during dis-/charge is demonstrated and shown to be coupled with electrolyte decomposition and conductive carbon oxidation, regardless of electrolyte salt concentration. The study provides deeper understanding of interfacial chemistry of active materials under variable proton activity in aqueous electrolytes, hence guiding the design of more effective electrode/electrolyte interfaces for ALIBs and beyond.
RESUMO
The investigation into intercalation mechanisms in vanadium pentoxide has garnered significant attention within the realm of research, primarily propelled by its remarkable theoretical capacity for energy storage. This comprehensive review delves into the latest advancements that have enriched our understanding of these intricate mechanisms. Notwithstanding its exceptional storage capacity, the compound grapples with challenges arising from inherent structural instability. Researchers are actively exploring avenues for improving electrodes, with a focus on innovative structures and the meticulous fine-tuning of particle properties. Within the scope of this review, we engage in a detailed discussion on the mechanistic intricacies involved in ion intercalation within the framework of vanadium pentoxide. Additionally, we explore recent breakthroughs in understanding its intercalation properties, aiming to refine the material's structure and morphology. These refinements are anticipated to pave the way for significantly enhanced performance in various energy storage applications.
RESUMO
Li-containing alloys and metallic deposits offer substantial Li+ storage capacities as alternative anodes to commercial graphite. However, the thermodynamically in sequence, yet kinetically competitive mechanism between Li solubility in the solid solution and intermediate alloy-induced Li deposition remains debated, particularly across the multiple scales. The elucidation of the mechanism is rather challenging due to the dynamic alloy evolution upon the non-equilibrium, transient lithiation processes under coupled physical fields. Here, influential factors governing Li solubility in the Li-Zn alloy are comprehensively investigated as a demonstrative model, spanning from the bulk electrolyte solution to the ion diffusion within the electrode. Through real-time phase tracking and spatial distribution analysis of intermediate alloy/Li metallic species at varied temperatures, current densities and particle sizes, the driving force of Li solubility and metallic plating along the Li migration pathway are probed in-depth. This study investigates the correlation between kinetics (pronounced concentration polarization, miscibility gap in lattice grains) and rate-limiting interfacial charge transfer thermodynamics in dedicating the Li diffusion into the solid solution. Additionally, the lithiophilic alloy sites with the balanced diffusion barrier and Li adsorption energy are explored to favor the homogeneous metal plating, which provides new insights for the rational innovation of high-capacity alloy/metallic anodes.
RESUMO
In this bibliometric study, we analyze two of the six battery research subfields identified in the BATTERY 2030+ roadmap: Materials Acceleration Platform and Smart functionalities: Sensing. In addition, we analyze the entire research field related to BATTERY 2030+ as a whole. We (a) evaluate the European standing in the two subfields/the BATTERY 2030+ field in comparison to the rest of the world, and (b) identify strongholds of the two subfields/the BATTERY 2030+ field across Europe. For each subfield and the field as a whole, we used seed articles, i. e. articles listed in the BATTERY 2030+ roadmap or cited by such articles, in order to generate additional, similar articles located in an algorithmically obtained classification system. The output of the analysis is publication volumes, field normalized citation impact values with comparisons between country/country aggregates and between organizations, co-publishing networks between countries and organizations, and keyword co-occurrence networks.
RESUMO
The pursuit of new and better battery materials has given rise to numerous studies of the possibilities to use two-dimensional negative electrode materials, such as MXenes, in lithium-ion batteries. Nevertheless, both the origin of the capacity and the reasons for significant variations in the capacity seen for different MXene electrodes still remain unclear, even for the most studied MXene: Ti3C2 T x . Herein, freestanding Ti3C2 T x MXene films, composed only of Ti3C2 T x MXene flakes, are studied as additive-free negative lithium-ion battery electrodes, employing lithium metal half-cells and a combination of chronopotentiometry, cyclic voltammetry, X-ray photoelectron spectroscopy, hard X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy experiments. The aim of this study is to identify the redox reactions responsible for the observed reversible and irreversible capacities of Ti3C2 T x -based lithium-ion batteries as well as the reasons for the significant capacity variation seen in the literature. The results demonstrate that the reversible capacity mainly stems from redox reactions involving the T x -Ti-C titanium species situated on the surfaces of the MXene flakes, whereas the Ti-C titanium present in the core of the flakes remains electro-inactive. While a relatively low reversible capacity is obtained for electrodes composed of pristine Ti3C2 T x MXene flakes, significantly higher capacities are seen after having exposed the flakes to water and air prior to the manufacturing of the electrodes. This is ascribed to a change in the titanium oxidation state at the surfaces of the MXene flakes, resulting in increased concentrations of Ti(II), Ti(III), and Ti(IV) in the T x -Ti-C surface species. The significant irreversible capacity seen in the first cycles is mainly attributed to the presence of residual water in the Ti3C2 T x electrodes. As the capacities of Ti3C2 T x MXene negative electrodes depend on the concentration of Ti(II), Ti(III), and Ti(IV) in the T x -Ti-C surface species and the water content, different capacities can be expected when using different manufacturing, pretreatment, and drying procedures.
RESUMO
The necessity for large scale and sustainable energy storage systems is increasing. Lithium-ion batteries have been extensively utilized over the past decades for a range of applications including electronic devices and electric vehicles due to their distinguishing characteristics. Nevertheless, their massive deployment can be questionable due to use of critical materials as well as limited lithium resources and growing costs of extraction. One of the emerging alternative candidates is potassium-ion battery technology due to potassium's extensive reserves along with its physical and chemical properties similar to lithium. The challenge to develop anode materials with good rate capability, stability and high safety yet remains. Iron oxides are potentially promising anodes for both battery systems due to their high theoretical capacity, low cost and abundant reserves, which aligns with the targets of large-scale application and limited environmental footprint. However, they present relevant limitations such as low electronic conductivity, significant volume changes and inadequate energy efficiency. In this review, we discuss some recent design strategies of iron oxide-based materials for both electrochemical systems and highlight the relationships of their structure performance in nanostructured anodes. Finally, we outline challenges and opportunities for these materials for possible development of KIBs as a complementary technology to LIBs.
RESUMO
Li- and Mn-rich layered oxides are promising positive electrode materials for future Li-ion batteries. The presence of crystallographic features such as cation-mixing and stacking faults in these compounds make them highly susceptible to synthesis-induced structural changes. Consequently, significant variations exist in the reported structure of these compounds that complicate the understanding of how the crystallographic structure influences its properties. This work investigates the synthesis-structure relations for three widely investigated Li- and Mn-rich layered oxides: Li2MnO3, Li1.2Mn0.6Ni0.2O2 and Li1.2Mn0.54Ni0.13Co0.13O2. For each compound, the average structure is compared between two synthetic routes of differing degrees of precursor mixing and four annealing protocols. Furthermore, thermodynamic and synthesis-specific kinetic factors governing the equilibrium crystallography of each composition are considered. It was found that the structures of these compounds are thermodynamically metastable under the synthesis conditions employed. In addition to a driving force to reduce stacking faults in the structure, these compositions also exhibited a tendency to undergo structural transformations to more stable phases under more intense annealing conditions. Increasing the compositional complexity introduced a kinetic barrier to structural ordering, making Li1.2Mn0.6Ni0.2O2 and Li1.2Mn0.54Ni0.13Co0.13O2 generally more faulted relative to Li2MnO3. Additionally, domains with different degrees of faulting were found to co-exist in the compounds. This study offers insight into the highly synthesis-dependent subtle structural complexities present in these compounds and complements the substantial efforts that have been undertaken to understand and optimise its electrochemical properties.
RESUMO
The unusual physical and chemical properties of electrolytes with excessive salt contents have resulted in rising interest in highly concentrated electrolytes, especially for their application in batteries. Here, we report strikingly good electrochemical performance in terms of conductivity and stability for a binary electrolyte system, consisting of lithium bis(fluorosulfonyl)imide (LiFSI) salt and ethylene carbonate (EC) solvent. The electrolyte is explored for different cell configurations spanning both high-capacity and high-voltage electrodes, which are well known for incompatibilities with conventional electrolyte systems: Li metal, Si/graphite composites, LiNi0.33Mn0.33Co0.33O2 (NMC111), and LiNi0.5Mn1.5O4 (LNMO). As compared to a LiTFSI counterpart as well as a common LP40 electrolyte, it is seen that the LiFSI:EC electrolyte system is superior in Li-metal-Si/graphite cells. Moreover, in the absence of Li metal, it is possible to use highly concentrated electrolytes (e.g., 1:2 salt:solvent molar ratio), and a considerable improvement on the electrochemical performance of NMC111-Si/graphite cells was achieved with the LiFSI:EC 1:2 electrolyte both at the room temperature and elevated temperature (55 °C). Surface characterization with scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) showed the presence of thicker surface film formation with the LiFSI-based electrolyte as compared to the reference electrolyte (LP40) for both positive and negative electrodes, indicating better passivation ability of such surface films during extended cycling. Despite displaying good stability with the NMC111 positive electrode, the LiFSI-based electrolyte showed less compatibility with the high-voltage spinel LNMO electrode (â¼4.7 V vs Li+/Li).
RESUMO
The electrochemical potential difference (ΔµÌ ) is the driving force for the transfer of a charged species from one phase to another in a redox reaction. In Li-ion batteries (LIBs), ΔµÌ values for both electrons and Li-ions play an important role in the charge-transfer kinetics at the electrode/electrolyte interfaces. Because of the lack of suitable measurement techniques, little is known about how ΔµÌ affects the redox reactions occurring at the solid/liquid interfaces during LIB operation. Herein, we outline the relations between different potentials and show how ambient pressure photoelectron spectroscopy (APPES) can be used to follow changes in ΔµÌ e over the solid/liquid interfaces operando by measuring the kinetic energy (KE) shifts of the electrolyte core levels. The KE shift versus applied voltage shows a linear dependence of â¼1 eV/V during charging of the electrical double layer and during solid electrolyte interphase formation. This agrees with the expected results for an ideally polarizable interface. During lithiation, the slope changes drastically. We propose a model to explain this based on charge transfer over the solid/liquid interface.
RESUMO
Dual-ion batteries (DIBs) generally operate beyond 4.7 V vs Li+/Li0 and rely on the intercalation of both cations and anions in graphite electrodes. Major challenges facing the development of DIBs are linked to electrolyte decomposition at the cathode-electrolyte interface (CEI), graphite exfoliation, and corrosion of Al current collectors. In this work, X-ray photoelectron spectroscopy (XPS) is employed to gain a broad understanding of the nature and dynamics of the CEI built on anion-intercalated graphite cycled both in highly concentrated electrolytes (HCEs) of common lithium salts (LiPF6, LiFSI, and LiTFSI) in carbonate solvents and in a typical ionic liquid. Though Al metal current collectors were adequately stable in all HCEs, the Coulombic efficiency was substantially higher for HCEs based on LiFSI and LiTFSI salts. Specific capacities ranging from 80 to 100 mAh g-1 were achieved with a Coulombic efficiency above 90% over extended cycling, but cells with LiPF6-based electrolytes were characterized by <70% Coulombic efficiency and specific capacities of merely ca. 60 mAh g-1. The poor performance in LiPF6-containing electrolytes is indicative of the continual buildup of decomposition products at the interface due to oxidation, forming a thick interfacial layer rich in LixPFy, POxFy, LixPOyFz, and organic carbonates as evidenced by XPS. In contrast, insights from XPS analyses suggested that anion intercalation and deintercalation processes in the range from 3 to 5.1 V give rise to scant or extremely thin surface layers on graphite electrodes cycled in LiFSI- and LiTFSI-containing HCEs, even allowing for probing anions intercalated in the near-surface bulk. In addition, ex situ Raman, SEM and TEM characterizations revealed the presence of a thick coating on graphite particles cycled in LiPF6-based electrolytes regardless of salt concentration, while hardly any surface film was observed in the case of concentrated LiFSI and LiTFSI electrolytes.
RESUMO
In the quest for environmentally friendly and safe batteries, moving from fluorinated electrolytes that are toxic and release corrosive compounds, such as HF, is a necessary step. Here, the effects of electrolyte fluorination are investigated for full cells combining silicon-graphite composite electrodes with LiNi1/3Mn1/3Co1/3O2 (NMC111) cathodes, a viable cell chemistry for a range of potential battery applications, by means of electrochemical testing and postmortem surface analysis. A fluorine-free electrolyte based on lithium bis(oxalato)borate (LiBOB) and vinylene carbonate (VC) is able to provide higher discharge capacity (147 mAh gNMC -1) and longer cycle life at C/10 (84.4% capacity retention after 200 cycles) than a cell with a highly fluorinated electrolyte containing LiPF6, fluoroethylene carbonate (FEC) and VC. The cell with the fluorine-free electrolyte is able to form a stable solid electrolyte interphase (SEI) layer, has low overpotential, and shows a slow increase in cell resistance that leads to improved electrochemical performance. Although the power capability is limiting the performance of the fluorine-free electrolyte due to higher interfacial resistance, it is still able to provide long cycle life at C/2 and outperforms the highly fluorinated electrolyte at 40 °C. X-ray photoelectron spectroscopy (XPS) results showed a F-rich SEI with the highly fluorinated electrolyte, while the fluorine-free electrolyte formed an O-rich SEI. Although their composition is different, the electrochemical results show that both the highly fluorinated and fluorine-free electrolytes are able to stabilize the silicon-based anode and support stable cycling in full cells. While these results demonstrate the possibility to use a nonfluorinated electrolyte in high-energy-density full cells, they also address new challenges toward environmentally friendly and nontoxic electrolytes.
RESUMO
Promising theoretical capacities and high voltages are offered by Li-rich disordered rocksalt oxyfluoride materials as cathodes in lithium-ion batteries. However, as has been discovered for many other Li-rich materials, the oxyfluorides suffer from extensive surface degradation, leading to severe capacity fading. In the case of Li2VO2F, we have previously determined this to be a result of detrimental reactions between an unstable surface layer and the organic electrolyte. Herein, we present the protection of Li2VO2F particles with AlF3 surface modification, resulting in a much-enhanced capacity retention over 50 cycles. While the specific capacity for the untreated material drops below 100 mA h g-1 after only 50 cycles, the treated materials retain almost 200 mA h g-1. Photoelectron spectroscopy depth profiling confirms the stabilization of the active material surface by the surface modification and reveals its suppression of electrolyte decomposition.
RESUMO
The solid electrolyte interphase (SEI) is the most critical yet least understood component to guarantee stable and safe operation of a Li-ion cell. Herein, the early stages of SEI formation in a typical LiPF6 and organic carbonate-based Li-ion electrolyte are explored by operando surface-enhanced Raman spectroscopy, on-line electrochemical mass spectrometry, and electrochemical quartz crystal microbalance. The electric double layer is directly observed to charge as Li+ solvated by ethylene carbonate (EC) progressively accumulates at the negatively charged electrode surface. Further negative polarization triggers SEI formation, as evidenced by H2 evolution and electrode mass deposition. Electrolyte impurities, HF and H2O, are reduced early and contribute in a multistep (electro)chemical process to an inorganic SEI layer rich in LiF and Li2CO3. This study is a model example of how a combination of highly surface-sensitive operando characterization techniques offers a step forward to understand interfacial phenomena in Li-ion batteries.
RESUMO
To elucidate what properties control and practically limit ion transport in highly concentrated electrolytes (HCEs), the viscosity, ionic conductivity, ionicity, and transport numbers were studied for nine model electrolytes and connected to the rate capability in Li-ion battery (LIB) cells. The electrolytes employed the LiTFSI salt in three molar ratio concentrations; 1 : 2, 1 : 4, and 1 : 16 (LiTFSI:X) vs. solvents (X) with different permittivities; tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) and propylene carbonate (PC). While the low polarity MTBE creates liquid electrolytes, ion-pairing limits the ionic conductivity despite extremely low viscosities. For the less concentrated 1 : 16 LiTFSI:MTBE and 1 : 16 LiTFSI:THF electrolytes the ionic diffusivities decrease with increased temperature, a sign of aggregation, but still their ionic conductivities and LIB performance increase. In general, the low ionic conductivity and high viscosity both limit the use of HCEs in LIBs, and no compensating mechanism seems to be present.
RESUMO
With the potential of delivering reversible capacities of up to 300 mAh/g, Li-rich transition-metal oxides hold great promise as cathode materials for future Li-ion batteries. However, a cohesive synthesis-structure-electrochemistry relationship is still lacking for these materials, which impedes progress in the field. This work investigates how and why different synthesis routes, specifically solid-state and modified Pechini sol-gel methods, affect the properties of Li2MnO3, a compositionally simple member of this material system. Through a comprehensive investigation of the synthesis mechanism along with crystallographic, morphological, and electrochemical characterization, the effects of different synthesis routes were found to predominantly influence the degree of stacking faults and particle morphology. That is, the modified Pechini method produced isotropic spherical particles with approximately 57% faulting and the solid-state samples possessed heterogeneous morphology with approximately 43% faulting probability. Inevitably, these differences lead to variations in electrochemical performance. This study accentuates the importance of understanding how synthesis affects the electrochemistry of these materials, which is critical considering the crystallographic and electrochemical complexities of the class of materials more generally. The methodology employed here is extendable to studying synthesis-property relationships of other compositionally complex Li-rich layered oxide systems.
RESUMO
Rechargeable sodium-ion batteries have recently attracted renewed interest as an alternative to Li-ion batteries for electric energy storage applications, because of the low cost and wide availability of sodium resources. Thus, the electrochemical energy storage community has been devoting increased attention to designing new cathode materials for sodium-ion batteries. Here we investigate P2- Na0.78Co1/2Mn1/3Ni1/6O2 as a cathode material for sodium ion batteries. The main focus is to understand the mechanism of the electrochemical performance of this material, especially differences observed in redox reactions at high potentials. Between 4.2 V and 4.5 V, the material delivers a reversible capacity which is studied in detail using advanced analytical techniques. In situ X-ray diffraction reveals the reversibility of the P2-type structure of the material. Combined soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering demonstrates that Na deintercalation at high voltages is charge compensated by formation of localized electron holes on oxygen atoms.
RESUMO
Water-splitting photoanodes based on semiconductor materials typically require a dopant in the structure and co-catalysts on the surface to overcome the problems of charge recombination and high catalytic barrier. Unlike these conventional strategies, a simple treatment is reported that involves soaking a sample of pristine BiVO4 in a borate buffer solution. This modifies the catalytic local environment of BiVO4 by the introduction of a borate moiety at the molecular level. The self-anchored borate plays the role of a passivator in reducing the surface charge recombination as well as that of a ligand in modifying the catalytic site to facilitate faster water oxidation. The modified BiVO4 photoanode, without typical doping or catalyst modification, achieved a photocurrent density of 3.5â mA cm-2 at 1.23â V and a cathodically shifted onset potential of 250â mV. This work provides an extremely simple method to improve the intrinsic photoelectrochemical performance of BiVO4 photoanodes.
RESUMO
Operando ambient pressure photoelectron spectroscopy in realistic battery environments is a key development towards probing the functionality of the electrode/electrolyte interface in lithium-ion batteries that is not possible with conventional photoelectron spectroscopy. Here, we present the ambient pressure photoelectron spectroscopy characterization of a model electrolyte based on 1M bis(trifluoromethane)sulfonimide lithium salt in propylene carbonate. For the first time, we show ambient pressure photoelectron spectroscopy data of propylene carbonate in the liquid phase by using solvent vapor as the stabilizing environment. This enables us to separate effects from salt and solvent, and to characterize changes in electrolyte composition as a function of probing depth. While the bulk electrolyte meets the expected composition, clear accumulation of ionic species is found at the electrolyte surface. Our results show that it is possible to measure directly complex liquids such as battery electrolytes, which is an important accomplishment towards true operando studies.