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The separator with high Young's modulus can avoid the danger of large-sized dendrites, but regulating the chemical behavior of lithium (Li) at the separator/anode interface can effectively eliminate the dendrite issue. Herein, a polyimine aerogel (PIA) with accurate nitrogen (N) functional design is used as the functional separator in Li metal batteries to promote uniform Li nucleation and suppress the dendrite growth. Specifically, the imine (N1) and protonated tertiary amine (N2) sites in the molecular structure of the PIA are significantly different in electron cloud density (ECD) distribution. The N1 site with higher ECD and the N2 site with lower ECD tend to attract and repulse Li+ through electrostatic interactions, respectively. This synergy effect of the PIA separator accelerates the interfacial Li+ diffusion on the Li anode to sustain a uniform two-dimensional Li nucleation behavior. Meanwhile, the well-defined nanochannels of the PIA separator show high affinity to electrolyte and bring uniform Li+ flux for Li plating/stripping. Consequently, the dendrites are effectively suppressed by the PIA separator in routine carbonate electrolyte, and the Li metal batteries with the PIA separator exhibit high Coulombic efficiency and stable high-rate cycling. These findings demonstrate that the ingenious marriage of special chemical structure designs and hierarchical pores can enable the separator to affect the interfacial Li nucleation behavior.
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A functional coating layer (FCL) is widely applied in fast-charging lithium-ion batteries to improve the sluggish Li+ transport kinetics of traditional graphite anodes. However, blindly increasing the Li+ conductivity for FCL reduces the overall electron conductivity of the anodes. Herein, we decoupled the effect of La-doping on TiNb2O7 (TNO) in terms of the phase evolution, Li+/electron transport, and lithiation behavior, and then proposed a promising La0.1TNO FCL with balanced Li+/electron transport for a fast-charging graphite anode. By optimizing the doping concentration of La, more holes are introduced into the TNO as electron carriers without causing lattice distortion, thus maintaining the fast Li+ diffusion channel in TNO. As a result, the graphite with La0.1TNO FCL delivers an excellent capacity of 220.2 mAh g-1 (96.3% retention) after 450 cycles at 3 C, nearly twice that of the unmodified one.
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Lithium (Li) dendrite growth in a routine carbonate electrolyte (RCE) is the main culprit hindering the practical application of Li metal anodes. Herein, we realize the regulation of the LiPF6 decomposition pathway in RCE containing 1.0 M LiPF6 by introducing a "self-polymerizing" additive, ethyl isothiocyanate (EITC), resulting in a robust LiF-rich solid electrolyte interphase (SEI). The effect of 1 vol % EITC on the electrode/electrolyte interfacial chemistry slows the formation of the byproduct LixPOFy. Such a LiF-rich SEI with EITC polymer winding exhibits a high Young's modulus and a uniform Li-ion flux, which suppresses dendrite growth and interface fluctuation. The EITC-based Li metal cell using a Li4Ti5O12 cathode delivers a capacity retention of 81.4% over 1000 cycles at 10 C, outperforming its counterpart. The cycling stability of 1 Ah pouch cells was further evaluated under EITC. We believe that this work provides a new method for tuning the interfacial chemistry of Li metal through electrolyte additives.
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Reasonably elevating the working voltage (≥4.4â V vs. Li/Li+ ) of the cathode is one of the efficient approaches to maximize the energy density of lithium-ion batteries (LIBs). As a preferred partner for high-voltage LIB systems, localized high-concentration electrolyte (LHCE), characterized by a stronger Li solvation structure, less free solvent, and robust electrode/electrolyte interphase has attracted much attention in academic circles. Herein, we systematically studied the role of the diluent in LHCE on the formation of the cathode electrolyte interphase (CEI) and elucidated that the existing anion-diluent pairing in the inner Helmholtz plane (IHP) results in an uneven CEI and subsequent battery degradation under high voltage. A m-fluorotoluene (mFT) diluent was further employed in the LHCE containing lithium difluoro(oxalato)borate (LiDFOB) to facilitate a uniform and rich-anion-derived CEI, since the weaker interaction of HmFT -BDFOB - , as compared to the HHhydrofluoroether -BDFOB - , reduces the influence of mFT in IHP or initial CEI formation. Consequently, the mFT-dominated LHCE propels the high-voltage performance of LIBs one step forward, endowing a 4.6â V-class 1.2-Ah graphite||LiNi0.8 Co0.1 Mn0.1 O2 pouch cells a 90.4 % capacity retention after 130â cycles. Our study thus describes a new index affecting the CEI formation and proposes novel strategies to deeply optimize the high-voltage LIBs.
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Lithium iron phosphate (LFP)/graphite batteries have long dominated the energy storage battery market and are anticipated to become the dominant technology in the global power battery market. However, the poor fast-charging capability and low-temperature performance of LFP/graphite batteries seriously hinder their further spread. These limitations are strongly associated with the interfacial Li-ion transport. Here we report a wide-temperature-range ester-based electrolyte that exhibits high ionic conductivity, fast interfacial kinetics and excellent film-forming ability by regulating the anion chemistry of Li salt. The interfacial barrier of the battery is quantitatively unraveled by employing three-electrode system and distribution of relaxation time technique. The superior role of the proposed electrolyte in preventing Li0 plating and sustaining homogeneous and stable interphases are also systematically investigated. The LFP/graphite cells exhibit rechargeability in an ultrawide temperature range of -80°C to 80°C and outstanding fast-charging capability without compromising lifespan. Specially, the practical LFP/graphite pouch cells achieve 80.2% capacity retention after 1200 cycles (2 C) and 10-min charge to 89% (5 C) at 25°C and provides reliable power even at -80°C.
RESUMO
Graphite anodes are prone to dangerous Li plating during fast charging, but the difficulty to identify the rate-limiting step has made a challenging to eliminate Li plating thoroughly. Thus, the inherent thinking on inhibiting Li plating needs to be compromised. Herein, an elastic solid electrolyte interphase (SEI) with uniform Li-ion flux is constructed on graphite anode by introducing a triglyme (G3)-LiNO3 synergistic additive (GLN) to commercial carbonate electrolyte, for realizing a dendrite-free and highly-reversible Li plating under high rates. The cross-linked oligomeric ether and Li3 N particles derived from the GLN greatly improve the stability of the SEI before and after Li plating and facilitate the uniform Li deposition. When 51 % of lithiation capacity is contributed from Li plating, the graphite anode in the electrolyte with 5 vol.% GLN achieved an average 99.6 % Li plating reversibility over 100â cycles. In addition, the 1.2-Ah LiFePO4 | graphite pouch cell with GLN-added electrolyte stably operated over 150â cycles at 3â C, firmly demonstrating the promise of GLN in commercial Li-ion batteries for fast-charging applications.
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The difficulties to identify the rate-limiting step cause the lithium (Li) plating hard to be completely avoided on graphite anodes during fast charging. Therefore, Li plating regulation and morphology control are proposed to address this issue. Specifically, a Li plating-reversible graphite anode is achieved via a localized high-concentration electrolyte (LHCE) to successfully regulate the Li plating with high reversibility over high-rate cycling. The evolution of solid electrolyte interphase (SEI) before and after Li plating is deeply investigated to explore the interaction between the lithiation behavior and electrochemical interface polarization. Under the fact that Li plating contributes 40 % of total lithiation capacity, the stable LiF-rich SEI renders the anode a higher average Coulombic efficiency (99.9 %) throughout 240â cycles and a 99.95 % reversibility of Li plating. Consequently, a self-made 1.2-Ah LiNi0.5 Mn0.3 Co0.2 O2 | graphite pouch cell delivers a competitive retention of 84.4 % even at 7.2â A (6â C) after 150â cycles. This work creates an ingenious bridge between the graphite anode and Li plating, for realizing the high-performance fast-charging batteries.
RESUMO
Contact prelithiation is an important strategy to compensate the initial capacity loss of lithium-ion batteries. However, the dead Li generated from inadequate Li conversion reduces the cycling stability of rechargeable batteries. Herein a mono-solvent dimethyl carbonate (DMC) electrolyte was employed in contact prelithiation for the first time. We discover that the low-organic-content raw electrolyte interphase (REI) induced by this electrolyte on Li source and anode is a mixed ion/electron conductor. Therefore, electron channels can be maintained even when the Li source has been completely wrapped by the DMC-derived REI. As a result, an outstanding Li source utilization of 92.8 % and a negligible dead Li yield can be realized. This strategy renders batteries with a very high initial Coulombic efficiency (90.0 %) and an excellent capacity retention (94.9 %) over 210â cycles, highlighting the significance of REI for effective contact prelithiation.
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Most P2-type layered oxides suffer from multiple voltage plateaus, due to Na+/vacancy-order superstructures caused by strong interplay between Na-Na electrostatic interactions and charge ordering in the transition metal layers. Here, Mg ions are successfully introduced into Na sites in addition to the conventional transition metal sites in P2-type Na0.7[Mn0.6Ni0.4]O2 as new cathode materials for sodium-ion batteries. Mg ions in the Na layer serve as "pillars" to stabilize the layered structure, especially for high-voltage charging, meanwhile Mg ions in the transition metal layer can destroy charge ordering. More importantly, Mg ion occupation in both sodium and transition metal layers will be able to create "Na-O-Mg" and "Mg-O-Mg" configurations in layered structures, resulting in ionic O 2p character, which allocates these O 2p states on top of those interacting with transition metals in the O-valence band, thus promoting reversible oxygen redox. This innovative design contributes smooth voltage profiles and high structural stability. Na0.7Mg0.05[Mn0.6Ni0.2Mg0.15]O2 exhibits superior electrochemical performance, especially good capacity retention at high current rate under a high cutoff voltage (4.2 V). A new P2 phase is formed after charge, rather than an O2 phase for the unsubstituted material. Besides, multiple intermediate phases are observed during high-rate charging. Na-ion transport kinetics are mainly affected by elemental-related redox couples and structural reorganization. These findings will open new opportunities for designing and optimizing layer-structured cathodes for sodium-ion batteries.
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Lithium metal batteries (LMBs) with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes have garnered significant interest as next-generation energy storage devices due to their high energy density. However, the instability of their electrode/electrolyte interfaces in regular carbonate electrolytes (RCEs) results in a rapid capacity decay. To address this, a colloid electrolyte consisting of Li3P nanoparticles uniformly dispersed in the RCE is developed by a one-step synthesis. This design concurrently creates stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) on both electrode surfaces. The cathode interface derived from this colloid electrolyte significantly facilitates the decomposition of Li salts (LiPF6 and LiDFOB) on the cathode surface by weakening the P-F and B-F bonds. This in situ formed P/LiF-rich CEI effectively protects the NCM811 cathode from side reactions. Furthermore, the Li3P embedded in the SEI optimizes and homogenizes the Li-ion transport, enabling dendrite-free Li deposition. Compared to the RCE, the designed colloid electrolyte enables robust cathode and anode interfaces in NCM811||Li full cells, minimizing gas and dendrite formation, and delivering a superior capacity retention of 82% over 120 cycles at a 4.7 V cutoff voltage. This approach offers different insights into electrolyte regulation and explores alternative electrolyte shapes and formulations.
RESUMO
Constructing an artificial solid electrolyte interphase (ASEI) on Li metal anodes (LMAs) is a potential strategy for addressing the dendrite issues. However, the mechanical fatigue of the ASEI caused by stress accumulation under the repeated deformation from the Li plating/stripping is not taken seriously. Herein, this work introduces a mechanically interlocked [an]daisy chain network (DCMIN) into the ASEI to stabilize the Li metal/ASEI interface by combining the functions of energy dissipation and fast Li-ion transport. The DCMIN featured by large-range molecular motions is cross-linked via efficient thiol-ene click chemistry; thus, the DCMIN has flexibility and excellent mechanical properties. As an ASEI, the crown ether units in DCMIN not only interact with the dialkylammonium of a flexible chain, forming the energy dissipation behavior but also coordinate with Li ion to support the fast Li-ion transport in DCMIN. Therefore, a stable 2800 h-symmetrical cycling (1 mA cm-2) and an excellent 5 C-rate (full cell with LiFePO4) performance are achieved by DCMIN-based ASEI. Furthermore, the 1-Ah pouch cell (LiNi0.88Co0.09Mn0.03O2 cathode) with DCMIN-coated LMA exhibits improved capacity retention (88%) relative to the Control. The molecular design of DCMIN provides new insights into the optimization of an ASEI for high-energy LMAs.
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Hierarchical self-assembly with long-range order above centimeters widely exists in nature. Mimicking similar structures to promote reaction kinetics of electrochemical energy devices is of immense interest, yet remains challenging. Here, we report a bottom-up self-assembly approach to constructing ordered mesoporous nanofibers with a structure resembling vascular bundles via electrospinning. The synthesis involves self-assembling polystyrene (PS) homopolymer, amphiphilic diblock copolymer, and precursors into supramolecular micelles. Elongational dynamics of viscoelastic micelle solution together with fast solvent evaporation during electrospinning cause simultaneous close packing and uniaxial stretching of micelles, consequently producing polymer nanofibers consisting of oriented micelles. The method is versatile for the fabrication of large-scale ordered mesoporous nanofibers with adjustable pore diameter and various compositions such as carbon, SiO2, TiO2 and WO3. The aligned longitudinal mesopores connected side-by-side by tiny pores offer highly exposed active sites and expedite electron/ion transport. The assembled electrodes deliver outstanding performance for lithium metal batteries.
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Spatial hindrance of lithium polysulfide (LiPS) diffusion by inserting a barrier interlayer has been deemed as an effective strategy to restrict the shuttle effect in lithium-sulfur batteries (LSBs). However, the extra interlayer without reversible capacity production inevitably reduces the actual energy density of the battery. Herein, a freestanding α-MoO3 nanobelt interlayer with the decoration of TiN nanoparticles and carbon nanotubes (denoted as MCT) is established. To investigate the capacity compensation effect of the MCT during cell operations, X-ray absorption near-edge spectrometry is conducted. It is revealed that MoO3 can sustain a reversible Li intercalation/deintercalation in a voltage range of 1.8-2.8 V, providing 180 mAh g-1 of extra capacity for compensating sulfur cathode. In addition, the adsorption of the lithiated α-MoO3 toward LiPSs is further evaluated. By matching a high-loading sulfur cathode (3.0 mg cm-2), a superior capacity of 713.3 mAh g-1 can be retained after 100 cycles under the MCT assistance.
RESUMO
Sub-freezing temperature presents a significant challenge to the survival of current Li-ion batteries (LIBs) as it leads to low capacity retention and poor cell rechargeability. The electrolyte in commercial LIBs relies too heavily on ethylene carbonate (EC) to produce a stable solid electrolyte interphase (SEI) on graphite (Gr) anodes, but its high melting point (36.4 °C) severely restricts ion transport below 0 °C, causing energy loss and Li plating. Here, a class of EC-free electrolytes that exhibits remarkable low-temperature performance without compromising cell lifespan is reported. It is found that at sub-zero temperatures, EC forms highly resistive SEI that seriously impedes electrode kinetics, whereas EC-free electrolytes create a highly stable, low-impedance SEI through anion decomposition, which boosts capacity retention and eliminates Li plating during charging. Pouch-type LiCoO2 (LCO)|Gr cells with EC-free electrolytes sustain 900 cycles at 25 °C with 1 C charge/discharge, and LiNi0.85 Co0.10 Al0.05 O2 (NCA)|Gr cells last 300 cycles at -15 °C with 0.3 C charge, both among the best-performing in the literature under comparable conditions. Even at -50 °C, the NCA|Gr cell with EC-free electrolytes still delivers 76% of its room-temperature capacity, outperforming EC-based electrolytes.
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FBLN5, a member of the short fibulins in the fibulin family of extracellular matrix/matricellular proteins, is involved in interactions with components of the basement membrane and extracellular matrix proteins. It plays key roles in endothelial tissues in many vascular diseases. In this study, the relationship between FBLN5 and carotid atherosclerotic plaque stability as well as the regulatory roles of miRNAs were evaluated. Differential gene expression analyses and weighted gene co-expression network analysis (WGCNA) based on the GSE163154 dataset (including 16 samples without intraplaque hemorrhage and 27 samples with intraplaque hemorrhage) in GEO revealed that FBLN5 is related to plaque stability and is the most significantly differentially expressed gene. LASSO regression was used to evaluate genes obtained from the intersection of differentially expressed genes and clinically significant modules identified by WGCNA. A prediction model based on eight genes, including FBLN5, was constructed and showed an accuracy of 0.951 based on an ROC analysis. Low FBLN5 expression in plaque tissues was confirmed by immunohistochemistry and western blotting. GO (Gene Ontology) and KEGG (Kyoto Encyclopedia of Genes and Genomes) enrichment analyses showed that FBLN5 acted mainly by the maintenance of the cellular matrix and reactive oxygen species production. miRNAs upstream of these eight predictive genes, including FBLN5, were identified and used to construct a network diagram. These results revealed that hsa-mir-128 and hsa-mir-532-3p were upstream regulatory factors of FBLN5, as verified by PCR assays of human plaque tissues demonstrating that both miRNAs were significantly up-regulated. Therefore, FBLN5 may play an important role in carotid atherosclerosis via hsa-mir-128 and hsa-mir-532-3p as well as become an essential target for treatment.
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Contact prelithiation is strongly considered for compensating the initial capacity loss of lithium-ion batteries, exhibiting great potential for ultralong cycle life of working batteries and the application of large-scale energy-storage systems. However, the utilization of the sacrificial Li source for contact prelithiation is low (<65%). Herein the fundamental mechanism of contact prelithiation is described from the perspective of the Li source/anode interfaces by regulating the initial contact state, and a clear illustration of the pathogeny for capacity attenuation is successfully delivered. Specifically, creating plentiful electron channels is an access to making contact prelithiation with a higher Li utilization, as the mitigated local current density that reduces the etching of Li dissolution and SEI extension on electron channels. A vacuum thermal evaporation for depositing the Li film enables the contact interface to possess an adequate electron channel construction, rendering a Li utilization of 91.0%, and the dead Li yield is significantly reduced in a working battery.
RESUMO
A transformative concept of solid electrochemical corrosion has been put forward, in which solid-state electrolyte LiPON has been applied to replace the liquid one to prelithiate graphite with Li-metal. Thus, high prelithiation efficiency and low polarization of the treated anode can be obtained, with a unique mosaic structure left at the surface.
RESUMO
Electrochemical irreversibility and sluggish mobility of Na+ in the cathode materials result in poor cycle stability and rate capability for sodium-ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn-based tunnel-structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na0.44Mn0.95Mg0.05O2 with Mg2+ in the hinging Mn-O5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na0.44MnO2. The improvement is attribute to the enhanced Na+ diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron-based X-ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na0.44Mn0.95Mg0.05O2 is more electron-abundant in Mn 3d orbits near the Fermi level than that in Na0.44MnO2, leading to higher redox participation of Mn ions.
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Oxygen-redox of layer-structured metal-oxide cathodes has drawn great attention as an effective approach to break through the bottleneck of their capacity limit. However, reversible oxygen-redox can only be obtained in the high-voltage region (usually over 3.5 V) in current metal-oxide cathodes. Here, we realize reversible oxygen-redox in a wide voltage range of 1.5-4.5 V in a P2-layered Na0.7 Mg0.2 [Fe0.2 Mn0.6 â¡0.2 ]O2 cathode material, where intrinsic vacancies are located in transition-metal (TM) sites and Mg-ions are located in Na sites. Mg-ions in the Na layer serve as "pillars" to stabilize the layered structure during electrochemical cycling, especially in the high-voltage region. Intrinsic vacancies in the TM layer create the local configurations of "â¡-O-â¡", "Na-O-â¡" and "Mg-O-â¡" to trigger oxygen-redox in the whole voltage range of charge-discharge. Time-resolved techniques demonstrate that the P2 phase is well maintained in a wide potential window range of 1.5-4.5 V even at 10 C. It is revealed that charge compensation from Mn- and O-ions contributes to the whole voltage range of 1.5-4.5 V, while the redox of Fe-ions only contributes to the high-voltage region of 3.0-4.5 V. The orphaned electrons in the nonbonding 2p orbitals of O that point toward TM-vacancy sites are responsible for reversible oxygen-redox, and Mg-ions in Na sites suppress oxygen release effectively.
RESUMO
Lithium-sulfur (Li-S) batteries have been regarded as a promising candidate of secondary batteries to satisfy the enormous demand for electric vehicles and energy storage applications. However, Li-S batteries still suffer from severe capacity fading due to the shuttle effect of lithium polysulfides. Here, we develop a freestanding double-layer MoO3/carbon nanotube@S (FMC@S) membrane by hydrothermal and suction filtration strategy, without polymer binder and current collector substrate. FMC@S contains a polysulfide blocking layer and an active material layer. Except for S content, the two layers have the same components and are integrated together, so there is no distinct interface between the two layers, which can facilitate ion and electron transport. As a result, the FMC@S cathode delivers promising capacity retention and rate capability. The hierarchical integrated design provides a new strategy to develop high-performance flexible cathodes for Li-S batteries.