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Li-alloying reactions facilitate the incorporation of a large number of Li atoms into the crystalline structures of electrodes, such as black phosphorus (BP). However, the reactions inevitably induce multistep phase transitions characterized by drastic atomic rearrangements and lattice collapse. Despite many theoretical and experimental studies on alloying mechanisms, long-term debates persist regarding the structures of the intermediate phases, the accurate pathways of phase transitions, the formation of specific configurations, and alloying/dealloying reversibility. Here, through a combination of operando electron diffraction measurements and ab initio simulations at the atomic and electronic scales, we identify key factors that govern the severe structural changes during alloying-dealloying reactions in BP. P-P bonds of three-bond P atoms are continuously broken during lithiation, generating two-bond P atoms with a high ability to accept inserted electrons and Li ions. Consequently, the pristine layered structure in BP is transformed to P7 cages in Li3P7, which then evolve to chain configurations in LiP and finally to isolated P atoms in Li3P. Specifically, the preferential formation of the P7 cage results from its lowest binding energy with three Li ions compared to other cage isomers. Furthermore, only LiP can be reversibly transformed to the crystalline structure of Li3P7 during charge, but it is thermodynamically favorable for Li3P7 and Li3P intermediates to be delithiated to amorphous structures. Our findings offer unique insights into the alloying mechanisms and deepen the fundamental understanding of alloying anode systems.
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Electrocatalysis is generally confined to dynamic liquid-solid and gas-solid interfaces and is rarely applicable in solid-state reactions. Here, we report a paradigm shift strategy to exploit electrocatalysis to accelerate solid-state reactions in the context of lithium-ion batteries (LIBs). We employ heteroatom doping, specifically boron for silicon and sulfur for phosphorus, to catalyze electrochemical Li-alloying reactions in solid-state electrode materials. The preferential cleavage of polar dopant-host chemical bonds upon lithiation triggers chemical bond breaking of the host material. This solid-state catalysis, distinct from liquid and gas phases, requires a critical doping concentration for optimal performance. Beyond a critical concentration of â¼1 atom %, boron and sulfur doping drastically reduces activation energies and accelerates redox kinetics during lithiation/delithiation processes, leading to markedly enhanced rate performance in boron-doped silicon and sulfur-doped black/red phosphorus anode. Notably, a sulfur-doped black phosphorus anode coupled with a lithium cobalt oxide cathode achieves an ultrafast-charging battery, recharging 80% energy of a battery in 302 Wh kg-1 in 9 min, surpassing the thus far reported LIBs.
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Alloy anode materials have garnered unprecedented attention for potassium storage due to their high theoretical capacity. However, the substantial structural strain associated with deep potassiation results in serious electrode fragmentation and inadequate K-alloying reactions. Effectively reconciling the trade-off between low-strain and deep-potassiation in alloy anodes poses a considerable challenge due to the larger size of K-ions compared to Li/Na-ions. In this study, we propose a chemical bonding modulation strategy through single-atom modification to address the volume expansion of alloy anodes during potassiation. Using black phosphorus (BP) as a representative and generalizing to other alloy anodes, we established a robust P-S covalent bonding network via sulfur doping. This network exhibits sustained stability across discharge-charge cycles, elevating the modulus of K-P compounds by 74%, effectively withstanding the high strain induced by the potassiation process. Additionally, the bonding modulation reduces the formation energies of potassium phosphides, facilitating a deeper potassiation of the BP anode. As a result, the modified BP anode exhibits a high reversible capacity and extended operational lifespan, coupled with a high areal capacity. This work introduces a new perspective on overcoming the trade-off between low-strain and deep-potassiation in alloy anodes for the development of high-energy and stable potassium-ion batteries.
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Hard carbon materials have shown promising potential for sodium-ion storage due to accommodating larger sodium ions. However, as for lithium-ion storage, the challenge lies in tuning the high lithiation plateau capacities, which impacts the overall energy density. Here, hard carbon microspheres (HCM) are prepared by tailoring the cross-linked polysaccharide, establishing a comprehensive methodology to obtain high-performance lithium-ion batteries (LIBs) with long plateau capacities. The "adsorption-intercalation mechanism" for lithium storage is revealed combining in situ Raman characterization and ex situ nuclear magnetic resonance spectroscopy. The optimized HCM possesses reduced defect content, enriched graphitic microcrystalline, and low specific surface area, which is beneficial for fast lithium storage. Therefore, HCM demonstrates a high reversible capacity of 537 mAh g-1 with a significant low-voltage plateau capacity ratio of 55%, high initial Coulombic efficiency, and outstanding rate performance (152 mAh g-1 at 10 A g-1). Moreover, the full cell (HCM||LiCoO2) delivers outstanding fast-charging capability (4 min charge to 80% at 10 C) and impressive energy density of 393 Wh kg-1. Additionally, 80% reversible capacity can be delivered under -40 °C with competitive cycling stability. This work provides in-depth insights into the rational design of hard carbon structures with extended low-voltage plateau capacity for high energy LIBs.
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Li+ de-solvation at solid-electrolyte interphase (SEI)-electrolyte interface stands as a pivotal step that imposes limitations on the fast-charging capability and low-temperature performance of lithium-ion batteries (LIBs). Unraveling the contributions of key constituents in the SEI that facilitate Li+ de-solvation and deciphering their mechanisms, as a design principle for the interfacial structure of anode materials, is still a challenge. Herein, we conducted a systematic exploration of the influence exerted by various inorganic components (Li2CO3, LiF, Li3PO4) found in the SEI on their role in promoting the Li+ de-solvation. The findings highlight that Li3PO4-enriched SEI effectively reduces the de-solvation energy due to its ability to attenuate the Li+-solvent interaction, thereby expediting the de-solvation process. Building on this, we engineer Li3PO4 interphase on graphite (LPO-Gr) anode via a simple solid-phase coating, facilitating the Li+ de-solvation and building an inorganic-rich SEI, resulting in accelerated Li+ transport crossing the electrode interfaces and interphases. Full cells using the LPO-Gr anode can replenish its 80 % capacity in 6.5â minutes, while still retaining 70 % of the room temperature capacity even at -20 °C. Our strategy establishes connection between the de-solvation characteristics of the SEI components and the interfacial structure design of anode materials for high performance LIBs.
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Covalent organic framework (COF) materials with porous character and robust structure have significant applied implications for K-ion battery (KIB) anodes, but they are limited by the low reversible capacity and inferior rate capability. Here, based on theoretical calculations, we identified that a porous bulk COF featuring numerous pyrazines and carbonyls in the π-conjugated periodic skeleton could provide multiple accessible redox-active sites for high-performance potassium storage. Its porous structure with a surface-dominated storage mechanism enabled the fast and stable storage of K-ions. Its insolubility in organic electrolytes and small volumetric change after potassiation ensured a robust electrode for stable cycling. As a KIB anode, this bulk COF demonstrated an unprecedentedly outstanding combination of reversible capacity (423 mAh g-1 at 0.1 C), rate capability (185 mAh g-1 at 10 C), and cyclability. The theoretical simulation and comprehensive characterizations confirmed the active sites are contributed by CâO, CâN, and the cation-π effect.
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In view of their high lithium storage capability, phosphorus-based anodes are promising for lithium-ion batteries. However, the low reduction potential (0.74 V versus Li+ /Li) of the commonly used ethylene carbonate-based electrolyte does not allow the early formation of a solid electrolyte interphase (SEI) prior to the initial phosphorus alloying reaction (1.5 V versus Li+ /Li). In the absence of a protective SEI, the phosphorus anode develops cracks, creating additional P/electrolyte interfaces. This results in the loss of P and the formation of a discontinuous SEI, all of which greatly reduce the electrochemical performance of the anode. Here, the effect of solvent reduction potential on the structure of the SEI is investigated. It is found that solvents with a high reduction potential, such as fluoroethylene carbonate, decompose to form an SEI concomitantly with the P alloying reaction. This results in a continuous, mechanically robust, and Li3 PO4 -rich SEI with improved Li-ion conductivity. These attributes significantly improve the cyclic stability and rate performance of the phosphorus-based anode.
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Appling an electrochemical catalyst is an efficient strategy for inhibiting the shuttle effect and enhancing the S utilization of Li-S batteries. Carbon-based materials are the most common conductive agents and catalyst supports used in Li-S batteries, but the correlation between the diversity of hybridizations and sulfur reduction reaction (SRR) catalytic activity remains unclear. Here, by establishing two forms of carbon models, i.e., graphitic carbon (GC) and amorphous carbon (AC), we observe that the nitrogen atom doped in the GC possesses a higher local charge density and a lower Gibbs free energy towards the formation of polysulfides than in the AC. And the GC-based electrode consistently inherits considerably enhanced SRR kinetics and superior cycling stability and rate capability in Li-S batteries. Therefore, the function of carbon in Li-S batteries is not only limited as conductive support but also plays an unignorable contribution to the electrocatalytic activities of SRR.
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Carbon-based single metal atom catalysts (SACs) are being extensively investigated to improve the kinetics of the Li-S redox reaction, which is greatly important for batteries with cell-level energy densities >500 W h kg-1 . However, there are contradictory reports regarding the electrocatalytic activities of the different metal atoms and the role of the metal atom in LiS chemistry still remains unclear. This is due to the complex relationship between the catalytic behavior and the structure of carbon-based SACs. Here, the catalytic behavior and active-site geometry, oxidation state, and the electronic structure of different metal centers (Fe/Co/Ni) embedded in nitrogen-doped graphene, and having similar physicochemical characteristics, are studied. Combining X-ray absorption spectroscopy, density functional theory calculations, and electrochemical analysis, it is revealed that the coordination-geometry and oxidation state of the metal atoms are modified when interacting with sulfur species. This interaction is strongly dependent on the hybridization of metal 3d and S p-orbitals. A moderate hybridization with the Fermi level crossing the metal 3d band is more favorable for LiS redox reactions. This study thus provides a fundamental understanding of how metal atoms in SACs impact LiS redox behavior and offers new guidelines to develop highly active catalytic materials for high-performance LiS batteries.
Asunto(s)
Carbono , Metales , Carbono/química , Catálisis , Metales/química , Nitrógeno/química , Oxidación-ReducciónRESUMEN
Lithium metal batteries are vital devices for high-energy-density energy storage, but the Li metal anode is highly reactive with electrolyte and forms uncontrolled dendrite that can cause undesirable parasitic reactions and, thus, poor cycling stability and raise safety concerns. Despite remarkable progress to partially solve these issues, the Li metal still plates at the electrode/electrolyte interface where the parasitic reactions and dendrite formation invariably occur. Here, we demonstrate the inward-growth plating of Li atoms into a metal foil of thickness of tens of micrometers while avoiding surface deposition, which is driven by the reversible solid-solution-based alloy phase change. Lithiation of the solid-solution alloy phase allows the freshly generated Li atoms at the surface to sink into the metal foil, while the reversible alloy phase change is companied by the dealloying reaction during delithiation, which extracts Li atoms from inside of the metal foil. The yielded dendrite free Li anode produces an enhanced Coulombic efficiency of 99.5 ± 0.2% with a reversible capacity of 1660 mA h g-1 (3.3 mA h cm-2).
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When used as a current collector, aluminum foil (AF) is vulnerable to local anodic corrosion during the charge/discharge process, which can lead to the deterioration of lithium-ion batteries (LIBs). Herein, a graphene foil (GF) with high electrical conductivity (â¼5800 S cm-1) and low mass density (1.80 g cm-3) was prepared by reduction of graphene oxide foil with ultra-high temperature (2800 °C) annealing, and it exhibited significantly anodic corrosion resistance when serving as a current collector. Moreover, a LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode using GF as a current collector (NCM523/GF) demonstrated a gravimetric capacity of 137.3 mAh g-1 at 0.5 C based on the mass of the whole electrode consisting of the active material, carbon black, binder, and the current collector, which is 44.5% higher than that of the NCM523/AF electrode. Furthermore, the NCM523/GF electrode retains higher capacity at relatively faster rates, from 0.1 C to 5.0 C. Therefore, GF, a lightweight corrosion-resistant current collector, is expected to replace the current commercial metal current collectors in LIBs and to achieve high energy-density batteries.
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Black phosphorus (BP) is a desirable anode material for alkali metal ion storage owing to its high electronic/ionic conductivity and theoretical capacity. In-depth understanding of the redox reactions between BP and the alkali metal ions is key to reveal the potential and limitations of BP, and thus to guide the design of BP-based composites for high-performance alkali metal ion batteries. Comparative studies of the electrochemical reactions of Li+ , Na+ , and K+ with BP were performed. Exâ situ X-ray absorption near-edge spectroscopy combined with theoretical calculation reveal the lowest utilization of BP for K+ storage than for Na+ and Li+ , which is ascribed to the highest formation energy and the lowest ion diffusion coefficient of the final potassiation product K3 P, compared with Li3 P and Na3 P. As a result, restricting the formation of K3 P by limiting the discharge voltage achieves a gravimetric capacity of 1300â mAh g-1 which retains at 600â mAh g-1 after 50 cycles at 0.25â A g-1 .
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The most successful lithium-ion batteries (LIBs) based on ethylene carbonate electrolytes and graphite anodes still suffer from severe energy and power loss at temperatures below -20 °C, which is because of high viscosity or even solidification of electrolytes, sluggish de-solvation of Li+ at the electrode surface, and slow Li+ transportation in solid electrolyte interphase (SEI). Here, a coherent lithium phosphide (Li3P) coating firmly bonding to the graphite surface to effectively address these challenges is engineered. The dense, continuous, and robust Li3P interphase with high ionic conductivity enhances Li+ transportation across the SEI. Plus, it promotes Li+ de-solvation through an electron transfer mechanism, which simultaneously accelerates the charge transport kinetics and stands against the co-intercalation of low-melting-point solvent molecules, such as propylene carbonate (PC), 1,3-dioxolane, and 1,2-dimethoxyethane. Consequently, an unprecedented combination of high-capacity retention and fast-charging ability for LIBs at low temperatures is achieved. In full-cells encompassing the Li3P-coated graphite anode and PC electrolytes, an impressive 70% of their room-temperature capacity is attained at -20 °C with a 4 C charging rate and a 65% capacity retention is achieved at -40 °C with a 0.05 C charging rate. This research pioneers a transformative trajectory in fortifying LIB performance in cryogenic environments.
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Due to the designable structure and capacity, organic materials are promising candidates for lithium-ion batteries. Herein, we report a novel type of porous organic frameworks (POFs) based on the coupling reaction of diazonium salt as the anodes for lithium ion storage. The active center containing an azo group and the adjacent lithium-philic adsorption site is constructed to investigate the electrochemical behaviors and reaction mechanism. As synthesized POF material (named as POF-AN) exhibits high reversible lithium storage capacities of 523â mAh g-1 at 0.5â A g-1 and 445â mAh g-1 at 2.0â A g-1 after 1500â cycles, showing excellent cycle stability and rate performance. The detailed characterizations reveal that the azo group can act as an electrochemical active site that reversibly bonds with Li-ions, and the adjacent oxygen atoms can electrostatically adsorb with Li-ions to promote the lithium storage reaction. This adsorption-assisted three-atom redox center is beneficial to synergistically enhance the adsorption and intercalation of lithium ions, which can further improve the capacity and cycle stability. By replacing the precursor, it is also facile to synthesize more similar structure types. The reversible redox chemistry of the adsorption-assisted three-atom active center provides new opportunities for the development of long lifespan and high-rate organic anodes.
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Phosphorus-carbon anode materials for alkali-metal ion storage in rechargeable batteries can simultaneously achieve high-energy density and fast charging. The P-C-bonded structure in the phosphorus-carbon materials has been observed and acknowledged to be a critical structural feature that renders improved cycling stability and rate performance. However, the underlying mechanisms, especially the role played by P-C bonds, remain elusive. By combining computational simulations and spectroscopic characterizations, we reveal that the stability of P-C bonds is critical to the electrochemical performance. In the discharge process, P-P bonds are fragile, while the bonding state of the P-C bonds is almost unchanged since electrons were mainly received by the P atoms to form lone pairs. The preserved P-C clusters can effectively serve as a reunion center for the recovery of P-P bonds in the recharging process, leading to a moderate energy change and improved cycling reversibility and structural stability of the phosphorous for electrochemical energy storage.
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We demonstrated a rechargeable aqueous Al-S battery based on a water-in-salt electrolyte with the configuration AlâAl(OTF)3 + LiTFSI + HClâS/C. The superconcentrated LiTFSI trapped water molecules to inhibit the hydrolysis of aluminum polysulfides in the cathode, and the HCl additive provided a mild acidic environment to enable repeatable oxidation-reduction reactions in the anode.
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High-rate lithium (Li) ion batteries that can be charged in minutes and store enough energy for a 350-mile driving range are highly desired for all-electric vehicles. A high charging rate usually leads to sacrifices in capacity and cycling stability. We report use of black phosphorus (BP) as the active anode for high-rate, high-capacity Li storage. The formation of covalent bonds with graphitic carbon restrains edge reconstruction in layered BP particles to ensure open edges for fast Li+ entry; the coating of the covalently bonded BP-graphite particles with electrolyte-swollen polyaniline yields a stable solid-electrolyte interphase and inhibits the continuous growth of poorly conducting Li fluorides and carbonates to ensure efficient Li+ transport. The resultant composite anode demonstrates an excellent combination of capacity, rate, and cycling endurance.
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Graphene oxide (GO) suspensions in solvents are the most important feedstocks for preparing GO based composites, and the dispersion state of GO on the microscale in solvent is a dominating factor in determining the physical properties of GO based composites. However, the morphology of GO sheets in solvents has hardly been reported due to the limitation of the characterization methods. Here, we report that the sheet thickness and lateral size of GO in solution can be identified using optical microscopy (OM) within a couple of minutes. The dispersion states of GO, including stretched flakes, scrolls, crumbles, and agglomerates, can also be distinguished. Moreover, the dispersion states, which change with the pH value and ionic strength of the solvent, are closely related to the dispersion stability of the GO suspension and the morphology of the GO/PVA composite. We believe that the fast observation and identification of GO sheets and their structural features in solvents, enabled by OM, opens up a new avenue to studying GO based composite materials in liquids.
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In recent times, few-layer black phosphorus (BP) has attracted tremendous attention as a promising anode material for sodium-ion batteries due to its particular two-dimensional structure, good electron conductivity, and high theoretical capacity. The main disadvantages of BP-based materials are the lower practical specific capacity of the BP-based composite than expectation because of the low P atom utilization and the structural fracture due to the large volume expansion that occurs during sodiation/desodiation cycles. In this work, we report a ternary composite comprising BP, graphite, and polyaniline (BP-G/PANI) with a BP mass content of â¼65 wt %. The ternary composite provides an optimized ion pathway (electrolyte â PANI â BP-G â BP), which reduces the charge transfer resistance of the electrode. Also, further ex situ X-ray absorption spectroscopy measurements demonstrate that the presence of graphite in the BP-G composite allows a deep sodiation of BP and also leads to a higher sodiation/desodiation reversibility. In addition, the uniformly coated PANI also restricts the huge volume expansion of the BP electrode through discharge/charge processes, which promise the stable cycling performance of BP-G/PANI. Thus, our composite shows a high reversible gravimetric capacity of 1530 mAh gcompo.-1 at 0.25 A g-1 and a capacity retention of 520 mAh gcompo.-1 after 1000 cycles at a high current density of 4 A g-1.