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All-solid-state batteries (ASSBs) are safe, high-energy-storage systems. However, despite the progress achieved in the development of high-ionic-conductivity solid electrolytes (SEs), the power performance of ASSBs remains low because of the high interfacial impedances in composite cathodes. Therefore, understanding the interfacial factors is crucial for obtaining high power ASSBs. This study provides a quantitative analysis of the influence of these factors using impedance spectroscopy measurements, which enables the elucidation of the interfacial impedance values of two key parameters, the grain-boundary resistance (ri,gb) and charge-transfer resistance (ri/e). Systematic investigation revealed an unexpected increase in the cathodic resistance with the decrease in the size of the cathode active material (CAM) particles, indicating that even high-reaction-surface-area CAMs yield low ri/e but high ri,gb values owing to their high porosity, resulting in a trade-off relationship. In contrast, this phenomenon is unlikely to occur in liquid-electrolyte-based batteries. Notably, we discuss how composite cathode design impacts performances of stable, high-power, and high-energy ASSBs.
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Solid-state Li-metal batteries (based on solid-state electrolytes) offer excellent safety and exhibit high potential to overcome the energy-density limitations of current Li-ion batteries, making them suitable candidates for the rapidly developing fields of electric vehicles and energy-storage systems. However, establishing close solid-solid contact is challenging, and Li-dendrite formation in solid-state electrolytes at high current densities causes fatal technical problems (due to high interfacial resistance and short-circuit failure). The Li metal/solid electrolyte interfacial properties significantly influence the kinetics of Li-metal batteries and short-circuit formation. This review discusses various strategies for introducing anode interlayers, from the perspective of reducing the interfacial resistance and preventing short-circuit formation. In addition, 3D anode structural-design strategies are discussed to alleviate the stress caused by volume changes during charging and discharging. This review highlights the importance of comprehensive anode/electrolyte interface control and anode design strategies that reduce the interfacial resistance, hinder short-circuit formation, and facilitate stress relief for developing Li-metal batteries with commercial-level performance.
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All-solid-state Li-O2 batteries that use ceramic electrolytes have been suggested to overcome the limitations posed by the decomposition of organic electrolytes. However, these systems show a low discharge capacity and high overpotential because the discharge product Li2O2 has low electronic conductivity. In this study, all-solid-state planar-type Li-O2 cells were constructed using a lithium anode, a Li1·3Al0·3Ti1·7(PO4) (LATP) inorganic solid electrolyte, and an air electrode composed of a Pt grid pattern. The discharge/charge process was observed in real time in a humidified O2 environment for the first time, which clarified both the hydration process of the discharge products and the charging process of the hydrated discharge products. The discharge product (LiOH) could be easily hydrated in water, which would facilitate ion transport, thereby increasing the discharge capacity and discharge voltage (vs Li/Li+; from 2.96 to 3.4 V). Thus, Li-O2 cells with a high energy density and a capacity of 3600 mAh/gcathode were achieved using a planar Pt-patterned electrode in a humidified O2 environment. This study is the first to demonstrate the hydration of the discharge products of a Li-O2 cell in humidified O2. Based on a thorough understanding of the hydration phenomenon/mechanism, our findings suggest new strategies for developing high-energy-density all-solid-state Li-O2 batteries using a simple, easy-to-manufacture planar Pt-patterned cathode.
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Lithium metal batteries (LMBs) with inorganic solid-state electrolytes are considered promising secondary battery systems because of their higher energy content than their Li-ion counterpart. However, the LMB performance remains unsatisfactory for commercialization, primarily owing to the inability of the inorganic solid-state electrolytes to hinder lithium dendrite propagation. Here, using an Ag-coated Li6.4La3Zr1.7Ta0.3O12 (LLZTO) inorganic solid electrolyte in combination with a silver-carbon interlayer, we demonstrate the production of stable interfacially engineered lab-scale LMBs. Via experimental measurements and computational modelling, we prove that the interlayers strategy effectively regulates lithium stripping/plating and prevents dendrite penetration in the solid-state electrolyte pellet. By coupling the surface-engineered LLZTO with a lithium metal negative electrode, a high-voltage positive electrode with an ionic liquid-based liquid electrolyte solution in pouch cell configuration, we report 800 cycles at 1.6 mA/cm2 and 25 °C without applying external pressure. This cell enables an initial discharge capacity of about 3 mAh/cm2 and a discharge capacity retention of about 85%.
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Garnet-type Li7La3Zr2O12 (LLZO) solid electrolytes (SE) demonstrates appealing ionic conductivity properties for all-solid-state lithium metal battery applications. However, LLZO (electro)chemical stability in contact with the lithium metal electrode is not satisfactory for developing practical batteries. To circumvent this issue, we report the preparation of various doped cubic-phase LLZO SEs without vacancy formation (i.e., Li = 7.0 such as Li7La3Zr0.5Hf0.5Sc0.5Nb0.5O12 and Li7La3Zr0.4Hf0.4Sn0.4Sc0.4Ta0.4O12). The entropy-driven synthetic approach allows access to hidden chemical space in cubic-phase garnet and enables lower solid-state synthesis temperature as the cubic-phase nucleation decreases from 750 to 400 °C. We demonstrate that the SEs with Li = 7.0 show better reduction stability against lithium metal compared to SE with low lithium contents and identical atomic species (i.e., Li = 6.6 such as Li6.6La3Zr0.4Hf0.4Sn0.4Sc0.2Ta0.6O12). Moreover, when a Li7La3Zr0.4Hf0.4Sn0.4Sc0.4Ta0.4O12 pellet is tested at 60 °C in coin cell configuration with a Li metal negative electrode, a LiNi1/3Co1/3Mn1/3O2-based positive electrode and an ionic liquid-based electrolyte at the cathode|SE interface, discharge capacity retention of about 92% is delivered after 700 cycles at 0.8 mA/cm2 and 60 °C.
Assuntos
Fontes de Energia Elétrica , Lítio , Eletrólitos , Eletrodos , Condutividade ElétricaRESUMO
Lithium metal batteries using solid electrolytes are considered to be the next-generation lithium batteries due to their enhanced energy density and safety. However, interfacial instabilities between Li-metal and solid electrolytes limit their implementation in practical batteries. Herein, Li-metal batteries using tailored garnet-type Li7-xLa3-aZr2-bO12 (LLZO) solid electrolytes is reported, which shows remarkable stability and energy density, meeting the lifespan requirements of commercial applications. We demonstrate that the compatibility between LLZO and lithium metal is crucial for long-term stability, which is accomplished by bulk dopant regulating and dopant-specific interfacial treatment using protonation/etching. An all-solid-state with 5 mAh cm-2 cathode delivers a cumulative capacity of over 4000 mAh cm-2 at 3 mA cm-2, which to the best of our knowledge, is the highest cycling parameter reported for Li-metal batteries with LLZOs. These findings are expected to promote the development of solid-state Li-metal batteries by highlighting the efficacy of the coupled bulk and interface doping of solid electrolytes.
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The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive ruthenium-based composite is designed as a carbon-free cathode by first-principles calculations to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a notable increase in capacity. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density.
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Rechargeable calcium batteries have attracted increasing attention as promising multivalent ion battery systems due to the high abundance of calcium. However, the development has been hampered by the lack of suitable cathodes to accommodate the large and divalent Ca2+ ions at a high redox potential with sufficiently fast ionic conduction. Herein, we report a new intercalation host which presents 500 cycles with a capacity retention of 90% and a remarkable power capability at ~3.2 V (vs. Ca/Ca2+) in a calcium battery. The cathode material derived from Na0.5VPO4.8F0.7 is demonstrated to reversibly accommodate a large amount of Ca2+ ions, forming a series of CaxNa0.5VPO4.8F0.7 (0 < x < 0.5) phases without any noticeable structural degradation. The robust framework enables one of the smallest volume changes (1.4%) and the lowest diffusion barriers for Ca2+ among the cathodes reported to date, offering the basis for the outstanding cycle life and power capability.
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Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.
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Calcium-ion batteries (CIBs) are considered to be promising next-generation energy storage systems because of the natural abundance of calcium and the multivalent calcium ions with low redox potential close to that of lithium. However, the practical realization of high-energy and high-power CIBs is elusive owing to the lack of suitable electrodes and the sluggish diffusion of calcium ions in most intercalation hosts. Herein, it is demonstrated that calcium-ion intercalation can be remarkably fast and reversible in natural graphite, constituting the first step toward the realization of high-power calcium electrodes. It is shown that a graphite electrode exhibits an exceptionally high rate capability up to 2 A g-1 , delivering ≈75% of the specific capacity at 50 mA g-1 with full calcium intercalation in graphite corresponding to ≈97 mAh g-1 . Moreover, the capacity stably maintains over 200 cycles without notable cycle degradation. It is found that the calcium ions are intercalated into graphite galleries with a staging process. The intercalation mechanisms of the "calciated" graphite are elucidated using a suite of techniques including synchrotron in situ X-ray diffraction, nuclear magnetic resonance, and first-principles calculations. The versatile intercalation chemistry of graphite observed here is expected to spur the development of high-power CIBs.
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Co-intercalation reactions make graphite as promising anodes for sodium ion batteries, however, the high redox potentials significantly lower the energy density. Herein, we investigate the factors that influence the co-intercalation potential of graphite and find that the tuning of the voltage as large as 0.38 V is achievable by adjusting the relative stability of ternary graphite intercalation compounds and the solvent activity in electrolytes. The feasibility of graphite anode in sodium ion batteries is confirmed in conjunction with Na1.5VPO4.8F0.7 cathodes by using the optimal electrolyte. The sodium ion battery delivers an improved voltage of 3.1 V, a high power density of 3863 W kg-1both electrodes, negligible temperature dependency of energy/power densities and an extremely low capacity fading rate of 0.007% per cycle over 1000 cycles, which are among the best thus far reported for sodium ion full cells, making it a competitive choice in large-scale energy storage systems.
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The development of high-performance oxygen evolution reaction (OER) catalysts is crucial to achieve the clean production of hydrogen via water splitting. Recently, Co-based oxides have been intensively investigated as some of the most efficient and cost-effective OER catalysts. In particular, compositional tuning of Co-based oxides via doping or substitution is shown to significantly affect their catalytic activity. Nevertheless, the origin of this enhanced catalytic activity and the reaction mechanism occurring at catalytic active sites remain controversial. Theoretical investigations are performed on the electrocatalytic properties of pristine and transition metal (Fe, Ni, and Mn)-substituted Co oxides using first-principle calculations. A comprehensive evaluation of the doping effects is conducted by considering various oxygen local environments in the crystal structure, which helps elucidate the mechanism behind the doping-induced enhancement of Co-based catalysts. It is demonstrated that the local distortion induced by dopant cations remarkably facilitates the catalysis at a specific site by modulating the hydrogen bonding. In particular, the presence of Jahn-Teller-active Fe(IV) is shown to result in a substantial reduction in the overpotential at the initially inactive catalysis site without compromising the activity of the pristine active sites, supporting previous experimental observations of exceptional OER performance for Fe-containing Co oxides.
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Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li+/Na+ substitution during solvothermal ion-exchange synthesis of LixNa1.5-xVOPO4F0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na+ by Li+, leading to peculiar Na+/Li+/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.
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The development of a high-performance oxygen evolution reaction (OER) catalyst is pivotal for the practical realization of a water-splitting system. Although an extensive search for OER catalysts has been performed in the past decades, cost-effective catalysts remain elusive. Herein, an amorphous cobalt phyllosilicate (ACP) with layered crystalline motif prepared by a room-temperature precipitation is introduced as a new OER catalyst; this material exhibits a remarkably low overpotential (η ≈ 367 mV for a current density of 10 mA cm-2 ). A structural investigation using X-ray absorption spectroscopy reveals that the amorphous structure contains layered motifs similar to the structure of CoOOH, which is demonstrated to be responsible for the OER catalysis based on density functional theory calculations. However, the calculations also reveal that the local environment of the active site in the layered crystalline motif in the ACP is significantly modulated by the silicate, leading to a substantial reduction of η of the OER compared with that of CoOOH. This work proposes amorphous phyllosilicates as a new group of efficient OER catalysts and suggests that tuning of the catalytic activity by introducing redox-inert groups may be a new unexplored avenue for the design of novel high-performance catalysts.
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A highly active and stable non-Pt electrocatalyst for hydrogen production has been pursued for a long time as an inexpensive alternative to Pt-based catalysts. Herein, we report a simple and effective approach to prepare high-performance iron phosphide (FeP) nanoparticle electrocatalysts using iron oxide nanoparticles as a precursor. A single-step heating procedure of polydopamine-coated iron oxide nanoparticles leads to both carbonization of polydopamine coating to the carbon shell and phosphidation of iron oxide to FeP, simultaneously. Carbon-shell-coated FeP nanoparticles show a low overpotential of 71 mV at 10 mA cm-2, which is comparable to that of a commercial Pt catalyst, and remarkable long-term durability under acidic conditions for up to 10â¯000 cycles with negligible activity loss. The effect of carbon shell protection was investigated both theoretically and experimentally. A density functional theory reveals that deterioration of catalytic activity of FeP is caused by surface oxidation. Extended X-ray absorption fine structure analysis combined with electrochemical test shows that carbon shell coating prevents FeP nanoparticles from oxidation, making them highly stable under hydrogen evolution reaction operation conditions. Furthermore, we demonstrate that our synthetic method is suitable for mass production, which is highly desirable for large-scale hydrogen production.
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Here, we demonstrate that graphite can serve as a versatile electrode for various rechargeable battery types by reversibly accommodating solvated alkali ions (such as K, Na, and Li) through co-intercalation in its galleries. The co-intercalation of alkali ions is observed to occur via staging reactions. Notably, their insertion behaviors, including their specific capacity, are remarkably similar regardless of the alkali ion species despite the different solubility limits of K, Na, and Li ions in graphite. Nevertheless, the insertion potentials of the solvated alkali ions differ from each other and are observed to be correlated with the interlayer distance in the intercalated graphite gallery.
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Demand on the practical synthetic approach to the high performance electrocatalyst is rapidly increasing for fuel cell commercialization. Here we present a synthesis of highly durable and active intermetallic ordered face-centered tetragonal (fct)-PtFe nanoparticles (NPs) coated with a "dual purpose" N-doped carbon shell. Ordered fct-PtFe NPs with the size of only a few nanometers are obtained by thermal annealing of polydopamine-coated PtFe NPs, and the N-doped carbon shell that is in situ formed from dopamine coating could effectively prevent the coalescence of NPs. This carbon shell also protects the NPs from detachment and agglomeration as well as dissolution throughout the harsh fuel cell operating conditions. By controlling the thickness of the shell below 1 nm, we achieved excellent protection of the NPs as well as high catalytic activity, as the thin carbon shell is highly permeable for the reactant molecules. Our ordered fct-PtFe/C nanocatalyst coated with an N-doped carbon shell shows 11.4 times-higher mass activity and 10.5 times-higher specific activity than commercial Pt/C catalyst. Moreover, we accomplished the long-term stability in membrane electrode assembly (MEA) for 100 h without significant activity loss. From in situ XANES, EDS, and first-principles calculations, we confirmed that an ordered fct-PtFe structure is critical for the long-term stability of our nanocatalyst. This strategy utilizing an N-doped carbon shell for obtaining a small ordered-fct PtFe nanocatalyst as well as protecting the catalyst during fuel cell cycling is expected to open a new simple and effective route for the commercialization of fuel cells.
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Graphene flakes (GFs) with minimized defects and oxidation ratios are incorporated into polyethylene (PE) to enhance the moisture barrier. GFs produced involving solvothermal intercalation show extremely low oxidation rates (3.17%), and are noncovalently functionalized in situ, inducing strong hydrophobicity. The fabricated composite possesses the best moisture barrier performance reported for a polymer-graphene composite.
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The increasing use of lithium-ion batteries (LIBs) in high-power applications requires improvement of their high-temperature electrochemical performance, including their cyclability and rate capability. Spinel lithium manganese oxide (LiMn2O4) is a promising cathode material because of its high stability and abundance. However, it exhibits poor cycling performance at high temperatures owing to Mn dissolution. Herein we show that when stoichiometric lithium manganese oxide is coated with highly doped spinels, the resulting epitaxial coating has a hierarchical atomic structure consisting of cubic-spinel, tetragonal-spinel, and layered structures, and no interfacial phase is formed. In a practical application of the coating to doped spinel, the material retained 90% of its capacity after 800â cycles at 60 °C. Thus, the formation of an epitaxial coating with a hierarchical atomic structure could enhance the electrochemical performance of LIB cathode materials while preventing large losses in capacity.
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Herein, we explore the capacity degradation of dilithium rhodizonate salt (Li2C6O6) in lithium rechargeable batteries based on detailed investigations of the lithium de/insertion mechanism in Li2C6O6 using both electrochemical and structural ex situ analyses combined with first-principles calculations. The experimental observations indicate that the LixC6O6 electrode undergoes multiple two-phase reactions in the composition range of 2 ≤ x ≤ 6; however, the transformations in the range 2 ≤ x ≤ 4 involve a major morphological change that eventually leads to particle exfoliation and the isolation of active material. Through first-principles analysis of LixC6O6 during de/lithiation, it was revealed that particle exfoliation is closely related to the crystal structural changes with lithium deinsertion from C6O6 interlayers of the LixC6O6. Among the lithium ions found at various sites, the extraction of lithium from C6O6 interlayers at 2 ≤ x ≤ 4 decreases the binding force between the C6O6 layers, promoting the exfoliation of C6O6 layers and pulverization at the electrode, which degrades capacity retention.