Fast Capacity Research Articles

A Gradient Composite Structure Enables a Stable Microsized Silicon Suboxide-Based Anode for a High-Performance Lithium-Ion Battery.

The practical application of microsized anodes is hindered by severe volume changes and fast capacity fading. Herein, we propose a gradient composite strategy and fabricate a silicon suboxide-based composite anode (d-SiO@SiOx/C@C) consisting of a disproportionated microsized SiO inner core, a homogeneous composite SiOx/C interlayer (x ≈ 1.5), and a highly graphitized carbon outer layer. The robust SiOx/C interlayer can realize a gradient abatement of stress and simultaneously connect the inner SiO core and carbon outer layer through covalent bonds. As a result, d-SiO@SiOx/C@C delivers a specific capacity of 1023 mAh/g after 300 cycles at 1 A/g with a retention of >90% and an average Coulombic efficiency of >99.7%. A full cell assembled with a LiNi0.8Co0.15Al0.05O2 cathode displays a remarkable specific energy density of 569 Wh/kg based on total active materials as well as excellent cycling stability. Our strategy provides a promising alternative for designing structurally and electrochemically stable microsized anodes with high capacity.

Improving electrochemical performance of spinel-type Ni/Mn-based high-voltage cathode material for lithium-ion batteries via La-F co-doping combined with in-situ integrated perovskite LaMnO3 coating layer

Spinel-type LiNi0.5Mn1.5O4 (LNMO) can provide high-voltage and high theoretical specific capacity as cathode material for lithium-ion batteries (LIBs), thereby LNMO is particularly suitable for electric/hybrid electric vehicles that require high power. Unfortunately, both serious structural deformation derived from the Jahn-Teller effect of Mn3+ and decomposition of electrolyte during repetitive charge/discharge processes at high operating potential result in fast capacity fade. In this work, lanthanum and fluorine co-doping LiNi0.5La0.01Mn1.49O3.97F0.03 (LF-LNMO) is proposed to eliminate its inherent defects. Fluorine can suppress Jahn-Teller effect of Mn3+ by reducing the generation of Mn3+; La3+ ions in LF-LNMO play a role in solidly riveting atoms together in the structure, and LaMnO3 coating layer acts as a physical protection barrier suppressing adverse side reactions that may damage battery performance. Thanks to the synergistic effect derived from structural modification of F−, the pinning effect of La3+ ions, and LaMnO3 surface coating interface reconstruction, the LF-LNMO cathode provides the best cycling performance and rate performance among all investigated electrode materials. Such as, LF-LNMO cathode can provide 64.02% capacity retention after the 1000th cycle at 500 mA g−1 and 30 °C, which is much higher than that (25.56%) of the undoped LiNi0.5Mn1.5O4 (P-LNMO). Besides, LF-LNMO electrode also behaves the excellent high-temperature cycling performance. This work provides a new strategy enhancing structural stability of spinel-type Ni/Mn-based oxide and would motivate us to further devise and prepare high power cathode materials for LIBs.

An organic/inorganic Z-scheme heterojunction Yb-MOF/BiOBr for efficient photocatalytic removal of NO

The advantages of visible light-driven catalysts with good light absorption, fast charge separation rate and high redox capacity are compelling. However, conventional inorganic semiconductor, such as pure BiOBr (BOB), showed a rapid photogenerated carriers recombination rate and low solar energy utilization ability, which limited the practical application of its photocatalytic performance. In this work, a novel organic/inorganic interleaved (Z-scheme) heterojunction Yb-MOF/BiOBr (Yb-MOF/BOB) photocatalyst was successfully synthesized. Compared with a single component, the Yb-MOF/BOB heterojunction exhibited significantly enhanced performance in photocatalytic oxidation of NO under visible light. Among them, Yb-MOF/BOB-20 had the best photocatalytic NO removal effect, up to 6424 ppb/g, which was 2.8 times and 4.2 times that of BOB and Yb-MOF, respectively. Photoelectrochemical characterization confirmed that the formation of heterojunctions broadened the absorption sidebands and increased the charge transfer at the interfacial junction of Yb-MOF/BOB. Combined with UPS, ESR and in-situ DRIFTS analysis, possible photocatalytic mechanisms were revealed, in which the formation of the Yb-MOF/BOB heterostructure endowed its high charge mobility and strong redox ability. Therefore, this work provided an effective way for photocatalytic removal of NO, and offered new ideas for developing heterogeneous photocatalysts.

A Highly Effective Polysulfide-Trapping Approach for the Development of High Energy Density, Scalable Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are identified as one of the most promising next-generation battery technologies owing to their high theoretical specific energy, sustainability, and affordability. However, the commercialization of Li-S batteries has been hindered by severe technical challenges, including the lithium polysulfide (PS) dissolution/shuttling effect, a major cause of fast capacity degradation over cycling. We demonstrated that, for the first time, nanolayer polymer coated high surface area porous carbons (NPCs) were coated directly on sulfur electrodes (NPC-S), which led to a high specific capacity of ∼1,600 mAh g−1 approaching the theoretical specific capacity limit in the NPC-S based Li-S batteries. The NPC-S based Li-S batteries maintained their large initial specific capacity gain compared with the Baseline-S based Li-S batteries (control) over extended cycles. A follow-on study indicated that the NPC-S approach is a necessary and critical step to boost the near-theoretical specific capacity while being stabilized over long cycles with a synergistic strategy. Our experimental and computational results suggest that NPC coated on sulfur electrodes provides not only an effective and strong PS-trapping power but also an increased redox reaction kinetics for sulfur ↔ PS’s conversions during battery charge and discharge, rendering the realization of near-theoretical discharge specific capacity in the NPC-S based Li-S batteries. The findings presented in this study may inspire a new, simple, low-cost, and commercially scalable approach, without adding any appreciable dead weight or volume to the batteries, in the effort to tackle the technical challenges facing SOA Li-S batteries.

Green electrospun Janus membrane of polyether block amide (PEBA) doped with hierarchical magnesium hydrogen phosphate for the removal of pharmaceuticals and personal care products

It has been a challenge to prepared polyether block amide (PEBA) fibrous membrane via solution electrospinning. The only few reported methods though involved hazardous solvents and surfactants which were against the principle of green chemistry. In this work, uniform fibrous membrane of PEBA was successfully fabricated by solution electrospinning with a bio-based solvent dihydrolevoglucosenone (Cyrene). To further improve the mechanical strength and adsorption performance of the PEBA membrane, a hierarchical magnesium hydrogen phosphate (MgHPO4·1.2H2O, MHP) was synthesized to blend evenly into the PEBA matrix. A Janus MHP/PEBA membrane with one side of hydrophobic surface and the other side of hydrophilic surface was subsequently prepared, which exhibited fast adsorption, high capacity, good selectivity and reusability towards ibuprofen, acetaminophen, carbamazepine and triclosan. In addition, the Janus membrane showed high removal efficiency of the above contaminants in secondary wastewater effluent with good long term stability. It demonstrated that this Janus MHP/PEBA membrane had a good potential in practical wastewater treatment.

Lignin‐derived hard carbon anode with a robust solid electrolyte interphase for boosted sodium storage performance

AbstractHard carbon is regarded as a promising anode candidate for sodium‐ion batteries due to its low cost, relatively low working voltage, and satisfactory specific capacity. However, it still remains a challenge to obtain a high‐performance hard carbon anode from cost‐effective carbon sources. In addition, the solid electrolyte interphase (SEI) is subjected to continuous rupture during battery cycling, leading to fast capacity decay. Herein, a lignin‐based hard carbon with robust SEI is developed to address these issues, effectively killing two birds with one stone. An innovative gas‐phase removal‐assisted aqueous washing strategy is developed to remove excessive sodium in the precursor to upcycle industrial lignin into high‐value hard carbon, which demonstrated an ultrahigh sodium storage capacity of 359 mAh g−1. It is found that the residual sodium components from lignin on hard carbon act as active sites that controllably regulate the composition and morphology of SEI and guide homogeneous SEI growth by a near‐shore aggregation mechanism to form thin, dense, and organic‐rich SEI. Benefiting from these merits, the as‐developed SEI shows fast Na+ transfer at the interphases and enhanced structural stability, thus preventing SEI rupture and reformation, and ultimately leading to a comprehensive improvement in sodium storage performance.

Mg/Ta dual-site doping of high-nickel layered cathode material LiNi0.9Co0.1O2 for extended cycling and thermal stability

Due to its high specific capacity and low cost, high-nickel layered oxide LiNi0.9Co0.1O2 has found promising application as the cathode materials for lithium-ion batteries. However, the crystallographic instability induced by Li+/Ni2+ anti-site exchange, the interfacial parasitic reactions and the microcracking caused by internal stress jointly contribute to the mechano-chemical failure of LiNi0.9Co0.1O2, leading to its fast capacity decay and high thermal stability concern. In this regard, a Mg/Ta dual-site doping strategy was proposed for LiNi0.9Co0.1O2, for which Mg2+ was doped in situ during the synthesis of cathode precursor, while Ta5+ ions were incorporated after the precursor synthesis. This novel synthesis approach leads to unique dual-site occupations of Mg2+ and Ta5+ in the 3a and 3b crystallographic sites respectively. The Mg2+ ions residing in 3a site can function as pillar ions by preventing the Li+/Ni2+ anti-site exchange and inhibiting layered to rock-salt phase transition. The Ta5+ ions occupying 3b site not only leads to the expanded lithium layer spacing but also creates interfacial protection and well-ordered microstructure in LiNi0.9Co0.1O2. Consequently, the dual-site-doped LiNi0.9Co0.1O2 outperforms the pristine and single-site-doped samples. For instance, its full cell shows a greatly enhanced cycling stability from 57.3 % to 90.5 % after 300 cycles at 1C/1C and well improved thermal stability from 205.2 °C to 225.6 °C, compared to the pristine sample. This Mg/Ta dual-site doping strategy provides a facile and practical way to improve the electrochemical and thermal performances of high-nickel layered cathode material LiNi0.9Co0.1O2.

Light fraction of pitch realizes robust coating on silicon anodes: The inhibition of volume expansion by self-delithiation

Extreme volume expansion upon lithiation remains a key challenge for Silicon (Si)-based anode materials, which commonly results in electrochemi-mechanical degradation and subsequent fast capacity fading. Pitch-derived carbon coating is an efficient strategy to alleviate the expansion of Si. However, clarifying the relationship between the microstructures of pitch-derived carbon and its expansion confinements properties is still difficult due to the complexity of pitch composition. Herein, we develop core-shell Si@C anode materials with robust protective pitch-derived carbon coating by pitch fraction separation and confirm the expansion confinements properties is connected to molecular structure and weight of pitch fractions. Small and disordered microcrystalline units of light fractions confer high resilience to the derived carbon coating which is less prone to rupture. The compressive stress from resilience coating leads to the transformation of lithium-silicon alloys to amorphous silicon during the early stages of lithiation, which allows for reduction in the expansion of Si. The composites of light fractions derived carbon with Si exhibits the best cycling stability. This work provides new insights into the understanding of expansion confinements in silicon-carbon anode materials.

Acid-resisting covalent organic framework enabling high-efficiency palladium recovery from used palladium catalyst under strong acid

Pd recovery from used sources is now receiving growing attentions, due to its scarcity and important application in many fields, however, which is still seriously restricted by the lack available adsorbent that can effectively capture palladium (Pd) from strong acid (>3 M). To this end, we report herein an acid-resisting covalent organic framework (COF), namely ECUT-COF-20, for such use. This new adsorbent is found to perform a benchmark Pd recovery performance from 6 M acidity such as the fast adsorption kinetics (1 min) and high uptake capacity (181 mg/g). The breakthrough test from a Pd/C-digested solution is used to confirm its practical application, giving an exceptionally one-round 95 % Pd recovery efficiency. The mechanism, as unveiled by characterization and DFT calculation, is due to a spatial and functional separation in this adsorbent, which could consequently not only overcome the influence of strong acid, but also provide abundant hydrogen bonds for fixing Pd ions.

Tuning the Interface Stability of Nickel-Rich NCM Cathode Against Aggressive Structural Collapse via the Synergistic Effect of Additives.

Nickel-rich layered oxides are envisaged as one of the most promising alternative cathode materials for lithium-ion batteries, considering their capabilities to achieve ultrahigh energy density at an affordable cost. Nonetheless, with increasing Ni content in the cathodes comes a severe extent of Ni4+ redox side reactions on the interface, leading to fast capacity decay and structural stability fading over extended cycles. Herein, dual additives of bis(vinylsulfonyl)methane (BVM) and lithium difluorophosphate (LiDFP) are adopted to synergistically generate the F-, P-, and S-rich passivation layer on the cathode, and the Ni4+ activity and dissolution at high voltage are restricted. The sulfur-rich layer formed by the polymerization of BVM, combined with the Li3PO4 and LiF phases derived from LiDFP, alleviates the problems of increased impedance, cracks, and an irreversible H2-H3 phase transition. Consequently, the Ni-rich LiNixM1-xO2 (x > 0.95) button half-cell cycled in LiDFP + BVM electrolyte exhibits a significant discharging capacity of 181.4 mAh g-1 at 1 C (1 C = 200 mA g-1) with retention of 83.7% after 100 cycles, surpassing the performance of the commercial electrolyte (160.7 mAh g-1) with retention of 53.3%. Remarkably, the NCM95||graphite pouch cell exhibits a remarkable capacity retention of 95.5% after 200 cycles. This work inspires the rational design of electrolyte additives for ultrahigh-energy batteries with nickel-rich layered oxide cathodes.

Soft and flexible polyvinyl alcohol/pullulan aerogels with fast and high water absorption capacity for facial mask substrates

Facial mask substrates commonly used in skincare are often considered unhealthy and environmentally unfriendly due to their composition of premoistened nonwovens containing various preservatives. This study aims to address this issue by developing a preservative-free degradable aerogel made from polyvinyl alcohol (PVA)/pullulan (PUL) using a unidirectional freeze-drying method. The aerogels had ordered three-dimensional porous structures and exhibited desirable mechanical properties. They were soft and flexible in both dry and wet states, and their Young's moduli were comparable to that of human skin. The aerogels had high porosity, ranging from 93.0 % to 95.1 %, and exhibited a high water absorption rate and water absorption capacity (ranging from 7.5 g/g to 10.1 g/g). After 30 min of water evaporation, the aerogels showed excellent moisture retention, ranging from 88 % to 93 %. Additionally, the PVA/PUL aerogel efficiently loaded and released active ingredients, such as rapidly releasing ascorbic acid (> 90 % within 30 min). These findings suggest that the PVA/PUL aerogel has potential as a material for facial mask substrates.

Metal‐Organic Framework/Graphene Nanoplatelet Composite Increases Rate Performance of Lithium–Sulfur Batteries

The polysulfide (PS) shuttle mechanism (PSM) is one of the biggest problems of lithium–sulfur (Li–S) batteries, resulting in fast capacity fading and low Coulombic efficiency. Due to electrostatic interactions, polar materials can adsorb the PS intermediates on their surfaces, decreasing the PSM effect. These polar materials should also have high electronic conductivity and surface area to be used in sulfur cathodes of Li–S batteries. In this respect, metal‐organic frameworks (MOF) and their derivatives gain significant attention. In this work, UiO‐66/graphene nanoplatelet (GNP)/sulfur composites are prepared with different UiO‐66/GNP ratios to investigate the effect of MOF amount on the electrochemical performance of Li–S batteries. MOF amount in the composite does not significantly influence performance for moderate S loadings. In contrast, Li–S cells with higher MOF‐loaded cathodes present superior performance at higher sulfur loadings and C rates.

Activation of MnO6 Units via an Interfacial Electric Field: Electron Injection into Mn t2g for Rapid and Stable Sodium Ion Storage in CeO2/MnOx.

Manganese-based oxides (MnOx) suffer from sluggish charge diffusion kinetics and poor cycling stability in sodium ion storage. Herein, an interfacial electric field (IEF) in CeO2/MnOx is constructed to obtain high electronic/ionic conductivity and structural stability of MnOx. The as-designed CeO2/MnOx exhibits a remarkable capacity of 397 F g-1 and favorable cyclic stability with 92.13% capacity retention after 10,000 cycles. Soft X-ray absorption spectroscopy and partial density of states results reveal that the electrons are substantially injected into the Mn t2g orbitals driven by the formed IEF. Correspondingly, the MnO6 units in MnOx are effectively activated, endowing the CeO2/MnOx with fast charge transfer kinetics and high sodium ion storage capacity. Moreover, In situRaman verifies a remarkably increased structural stability of CeO2/MnOx, which is attributed to the enhanced Mn─O bond strength and efficiently stabilized MnO6 units. Mechanism studies show that the downshift of Mn 3d-band center dramatically increases the Mn 3d-O 2p orbitals overlap, thus inhibiting the Jahn-Teller (J-T) distortion of MnOx during sodium ion insertion/extraction. This work develops an advanced strategy to achieve both fast and sustainable sodium ion storage in metal oxides-based energy materials.

Conductive Metal-Organic Framework with Superior Redox Activity as a Stable High-Capacity Anode for High-Temperature K-Ion Batteries.

High-temperature rechargeable batteries are essential for energy storage in elevated-temperature situations. Due to the resource abundance of potassium, high-temperature K-ion batteries are drawing increasing research interest. However, raising the working temperature would aggravate the chemical and mechanical instability of the KIB anode, resulting in very fast capacity fading, especially when high capacity is pursued. Here, we demonstrated that a porous conductive metal-organic framework (MOF), which is constructed by N-rich aromatic molecules and CuO4 units via π-d conjugation, could provide multiple accessible redox-active sites and promised robust structure stability for efficient potassium storage at high temperatures. Even working at 60 °C, this MOF anode could deliver high initial capacity (455 mAh g-1), impressive rate, and extraordinary cyclability (96.7% capacity retention for 1600 cycles), which is much better than those of reported high-temperature KIB anodes. The mechanistic study revealed that C═N groups and CuO4 units contributed abundant redox-active sites; the synergistic effect of π-d conjugated character and reticular porous architecture facilitated the K+/e- transport and ensured an insoluble electrode with small volume deformation, thus achieving stable high-capacity potassium storage.

A multi-step fast charging-based battery capacity estimation framework of real-world electric vehicles

Accurately evaluating battery degradation is not only crucial for ensuring the safe and reliable operation of electric vehicles (EVs) but also fundamental for their intelligent management and maximum utilization. However, the non-linearity, non-measurability, and multi-stress coupled operating conditions have posed significant challenges for battery health prediction. This paper proposes a battery capacity estimation framework based on real-world operating data. Firstly, a comprehensive feature pool is constructed from the direct external features extracted during multi-step fast charging processes and the quantitative representation of operating conditions. Subsequently, a two-step feature engineering is introduced to select the most relevant features and eliminate the interference components. The battery capacity estimation framework is then implemented using machine learning methods. Validation results demonstrate that the proposed framework achieves superior estimation accuracy with lower computational expense compared to the modelling process without feature engineering. The MAPE and RMSE reach 1.18% and 1.98 Ah, respectively, representing reductions in errors of up to 8.53% and 11.21%. Collectively, the proposed framework paves the foundation for online health prognostics of batteries under practical operating conditions.

Advancements and Challenges in High-Capacity Ni-Rich Cathode Materials for Lithium-Ion Batteries.

Nowadays, lithium-ion batteries are undoubtedly known as the most promising rechargeable batteries. However, these batteries face some big challenges, like not having enough energy and not lasting long enough, that should be addressed. Ternary Ni-rich Li[NixCoyMnz]O2 and Li[NixCoyAlz]O2 cathode materials stand as the ideal candidate for a cathode active material to achieve high capacity and energy density, low manufacturing cost, and high operating voltage. However, capacity gain from Ni enrichment is nullified by the concurrent fast capacity fading because of issues such as gas evolution, microcracks propagation and pulverization, phase transition, electrolyte decomposition, cation mixing, and dissolution of transition metals at high operating voltage, which hinders their commercialization. In order to tackle these problems, researchers conducted many strategies, including elemental doping, surface coating, and particle engineering. This review paper mainly talks about origins of problems and their mechanisms leading to electrochemical performance deterioration for Ni-rich cathode materials and modification approaches to address the problems.

Adsorption of Safranine-T dye using a waste-based zeolite: Optimization, kinetic and isothermal study

The global issue of water resource pollution due to wastewater containing dyes is a significant environmental concern. The proper treatment of these harmful wastewaters is a great challenge due to their characteristic structural complexity and low biodegradability. The present work reports the application of a Linde Type-A (LTA) zeolite synthesized from a hazardous aluminum waste as an adsorbent to remediate Safranine-T dye from aqueous solutions. The optimal experimental conditions (agitation rate and zeolite dosage of 147 rpm and 21.5 g/L, respectively) were determined through a central composite rotational design (CCRD), and enabled a removal efficiency of 98.12 % of the textile dye. The model that showed the best fit to the experimental data and better explained the adsorption mechanism, according to the isothermal studies, was the Sips model. The kinetics followed the pseudo-first order model and revealed that Safranine-T dye removal was achieved in a contact time of just one minute. The waste-based LTA zeolite exhibited highly promising adsorbent properties with an efficient and extremely fast adsorption capacity. Its use as a treatment agent for dye-contaminated wastewater can significantly contribute to sustainability and the circular economy.

Uniform Al Doping in LiCoO2 for 4.55 V Lithium-Ion Pouch Cells.

As the classic cathode material, lithium cobalt oxide (LiCoO2, LCO) suffers from severe structural and interfacial degradation at voltage >4.5 V, which induces fast capacity decay of the cells. Herein, we adopt a simple and effective method, doping aluminum (Al) cations in precursors, to improve the structural stability of LCO and systematically investigate the effect of Al doping on the electrochemical performances. Doping in precursors rather than bulk particles is beneficial to realize uniform Al ions distribution. Even at 4.5 V charging voltage, the LCO/graphite pouch cells with high Al doping levels (8500 ppm) deliver initial and reversible discharge capacities of 386 and 369 mAh after 500 cycles, respectively. The capacity retention is as high as 95.5%. When the cutoff voltage reaches 4.55 V, the pouch cell maintains 79.0% of the first-cycle discharge capacity after 500 cycles. With optimized electrolyte, the pouch cell realizes 87.3% of the initial discharge capacity after 500 cycles at 45 °C. Moreover, the thermal safety performance of the pouch cells with Al doping is promising. Our work displays an excellent inspiration for developing high-voltage, long-cycle, and safe LCO cathode for commercial lithium-ion batteries.

Chemo-mechanical failure mechanisms of the silicon anode in solid-state batteries.

Silicon is a promising anode material due to its high theoretical specific capacity, low lithiation potential and low lithium dendrite risk. Yet, the electrochemical performance of silicon anodes in solid-state batteries is still poor (for example, low actual specific capacity and fast capacity decay), hindering practical applications. Here the chemo-mechanical failure mechanisms of composite Si/Li6PS5Cl and solid-electrolyte-free silicon anodes are revealed by combining structural and chemical characterizations with theoretical simulations. The growth of the solid electrolyte interphase at the Si|Li6PS5Cl interface causes severe resistance increase in composite anodes, explaining their fast capacity decay. Solid-electrolyte-free silicon anodes show sufficient ionic and electronic conductivities, enabling a high specific capacity. However, microscale void formation during delithiation causes larger mechanical stress at the two-dimensional interfaces of these anodes than in composite anodes. Understanding these chemo-mechanical failure mechanisms of different anode architectures and the role of interphase formation helps to provide guidelines for the design of improved electrode materials.

Modeling and Operating Characteristics of Excitation System for Variable Speed Pumped Storage Unit with Full-Size Converter

The variable speed pumped storage unit with a full-size converter (FSC-VSPSU) can provide fast and flexible regulation capacity for the power grid, assisting the rapid development of the new energy-dominated power systems, and its application is gradually becoming widespread. The excitation system of FSC-VSPSU is crucial for maintaining the motor-port voltage and further supports the stable operation of the entire unit. However, there is currently no research on excitation system modeling, and their essential operating characteristics have not been discussed in detail, which needs further study. With this aim, this paper firstly establishes a detailed transfer function model for FSC-VSPSU, which is then used to study the influence rules of FSC-VSPSU parameters on the operating characteristics. In addition, based on the summarized operating characteristics, the excitation system can be optimized, and its complexity is greatly reduced while ensuring the original performance of the unit. Finally, the results of the simulation can verify the correctness of the established model and the explored operating characteristics.