Search Results (185)

Silicon oxide–graphite is a promising high-capacity anode material for next-generation lithium-ion batteries (LIBs). However, despite using a small fraction (≤5%) of Si, it suffers from a short cycle life owing to intrinsic swelling and particle pulverization during cycling, making practical application challenging. High-nickel (Ni ≥ 80%) oxide cathodes for high-energy-density LIBs and their operation beyond 4.2 V have been pursued, which requires the anodic stability of the electrolyte. Herein, we report a nonflammable multi-functional fluorinated ester–based liquid electrolyte that stabilizes the interfaces and suppresses the swelling of highly loaded 5 wt% SiO–graphite anode and LiNi_0.88Co_0.08Mn_0.04O₂ cathode simultaneously in a 3.5 mAh cm⁻² full cell, and improves cycle life and battery safety. Surface characterization results reveal that the interfacial stabilization of both the anode and cathode by a robust and uniform solid electrolyte interphase (SEI) layer, enriched with fluorinated ester-derived inorganics, enables 80% capacity retention of the full cell after 250 cycles, even under aggressive conditions of 4.35 V, 1 C and 45 °C. This new electrolyte formulation presents a new opportunity to advance SiO-based high-energy density LIBs for their long operation and safety. Full article

Separators are generally considered inert components in lithium-ion batteries. In the past, some electroactive polymers have been successfully applied in separator modifications for overcharge protection or as acid scavengers. This study highlights the first use of two “electroactive” carbazole polymers (copolymer 9-phenyl-9H-carbazole-phenyl [PCP] and poly(9-vinylcarbazole) [PVC]), which were each applied separately as coatings on the cathode-facing side of commercial Celgard 2325 separators, respectively, to enhance the cycling performance of 0.3Li₂MnO₃·0.7LiMn_0.5Ni_0.5O₂//graphite (LMR-NM//Gr) full cells through interphase engineering. The team observed an irreversible polymer oxidation process of the carbazole-functionalized polymers—occurring only during the first charge—for the modified separator cells, and the results were confirmed by dQ/dV analysis, cyclic voltammetry measurements, and nuclear magnetic resonance characterizations. During this oxidation, carbazole polymers participate in the process of interphase formation, contributing to the improved cycling performance of LMR-NM//Gr batteries. Particularly, oxidation takes place at voltages of ~4.0 and ~3.5 V when PCP and PVC are used as separator coatings, which is highly irreversible. Further postmortem examinations suggest that the improvements using these modified separators arise from the formation of higher-quality and more inorganic SEI, as well as the beneficial CEI enriched in LixPOyFz. These interphases effectively inhibit the crosstalk effect by reducing TM dissolution. Full article

High-voltage spinel (LiNi_0.5Mn_1.5O₄; LNMO) has been a prospective cathode material that may exploit the maximal voltage of 5 V for lithium-ion batteries. However, the practical application has been hindered by the severe electrochemical instability of the Ni²⁺/Ni⁴⁺ redox couple at such a high voltage. Herein, we coated lithium phosphate (Li₃PO₄) on the surface of the LNMO by a wet-coating method to improve the electrochemical stability. The coating layer provided an effective cathode–electrolyte interphase, which prevented the excessive decomposition of the electrolyte on the surface of LNMO cathode. The Li₃PO₄-coated LNMO exhibited enhanced rate capability in accordance with the lowered solid-electrolyte interphase (SEI) and charge-transfer resistance values from electrochemical impedance spectroscopy. Full article

Iron phosphate (FePO₄·2H₂O) was synthesized via anodic oxidation using nickel–iron alloy composition simulates from laterite nickel ore as the anode and graphite electrodes as the cathode, with phosphoric acid serving as the electrolyte. A uniform experimental design was employed to systematically optimize the synthesis parameters including voltage, electrolyte concentration, electrolysis time, and degree of acidity or alkalinity (pH). The results indicate that the addition of cetyltrimethylammonium bromide (CTAB) surfactant effectively modulated the morphology of the anodic oxidation products. The optimized conditions were determined to be an electrolyte concentration of 1.2 mol/L, a voltage of 16 V, a pH of 1.6, an electrolysis time of 8 h, and a 3% CTAB addition. Under these conditions, the synthesized FePO₄·2H₂O exhibited enhanced performance as a lithium-ion battery precursor. Specifically, the corresponding LiFePO₄/C cathode delivered an initial discharge capacity of 157 mA h g⁻¹ at 0.2 C, retaining 99.36% capacity after 100 cycles. These findings provide valuable insights and theoretical foundations for the efficient preparation of iron phosphate precursors, highlighting the significant impact of optimized synthesis conditions on the electrochemical performance of lithium iron phosphate. Full article

Li-rich Mn-based cathode materials are considered potential cathode materials for next-generation lithium-ion batteries due to their outstanding theoretical capacity and energy density. Nonetheless, challenges like oxygen loss, transition metal migration, and structural changes during cycling have limited their potential for commercialization. The work in this study employed a straightforward heat treatment to generate oxygen vacancies. This process led to the development of a spinel phase on the surface, which improved Li⁺ diffusion and boosted the electrochemical performance of Li-rich Mn-based oxides. The results demonstrate that the treated Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ exhibits an initial specific capacity of 247 mAh·g⁻¹ at 0.2C, as well as a reversible capacity of 224 mAh·g⁻¹ after 100 cycles, with a capacity retention of 90.7%. The voltage decay is 1.221 mV per cycle under 1C long-term cycling conditions, indicating excellent cycling stability and minimal voltage drop. Therefore, this strategy of engineering through nanoscale oxygen vacancies provides a new idea for the development of high-stability layered oxide anodes and provides a reference for the development and application of new energy materials. Full article

The poor thermal stability of polypropylene (PP) separators poses risks of electrolyte leakage and battery short-circuiting, limiting their application in lithium metal batteries (LMBs). To address these challenges, a gel polymer membrane was designed using polymer blending technology. This membrane effectively retains the electrolyte, provides a stable environment, enhances thermal stability, and significantly decreases the risk of battery explosions and side reactions between the lithium metal and the electrolyte. Compared to commercial PP separators, the developed blend-type gel polymer electrolyte (b-GPE) demonstrates a superior performance, including structural stability at temperatures up to 150 °C and a high lithium-ion transference number ($t_{{Li}^{+}}$) of 0.513. Furthermore, a cell with a LiCoO₂ cathode operated at a 1 C rate retains 97.4% of its capacity after 300 cycles. After exposure to 120 °C, the b-GPE-120 demonstrates that its performance is comparable to that of the b-GPE, such as a $t_{{Li}^{+}}$ of 0.506, a high electrolyte absorption rate, and a wide electrochemical window of 5.2 V. Full article

All-solid-state lithium-ion batteries (ASSLBs) are attractive energy storage devices because of their excellent gravimetric and volumetric capacity and ability to supply high power rates. Porous silicon (Si) is a promising material for an anode in lithium-ion batteries due to its high capacity and low discharge potential. However, Si anodes cause significant problems due to strong volume growth during the lithiation and delithiation processes, which results in rapid capacity fading and poor cycle stability. To overcome this problem, we developed mesoporous silica (SiO₂) aerogels into porous silicon (Si) anodes using a magnesiothermic reduction (MTR) process. By effectively preserving the porous structure, this approach enables the material to endure volume fluctuations while maintaining its structural integrity during cycling. In our study, we demonstrated a feasible approach to fabricate the porous silicon (Si) from hydrophobic and hydrophilic silica (SiO₂) aerogel and magnesium powder (Mg) through the MTR process at 600~900 °C. The sample obtained after the reduction process was treated with hydrochloric acid (HCl) to remove byproducts. As prepared, Si was characterized using various techniques, including XRD, XRF, FT-IR, XPS, SEM, and BET, which confirmed the successful production, chemical purity, and structural retention of Si. Furthermore, the coin cell was fabricated using Si as an anode, and the electrochemical performance was analyzed. The charge/discharge cycling tests at 1 C and 0.02~2 V (vs. the Li condition) revealed the effects of silicon content, wettability, and interfacial compatibility on electrode performance. Conversely, for better understanding, a long-term cycling test was conducted at 1 C rate, 0–1.5 V (vs. Li) to evaluate capacity retention. Our findings highlight the potential application of silicon (Si) aerogels produced from silica (SiO₂) aerogels by magnesiothermic reduction to improve lithium-ion battery performance. Full article

Localized high-concentration electrolytes (LHCEs) are promising systems for improving the high-voltage performance and interfacial stability of lithium-metal batteries (LMBs). Unfortunately, they are always challenged by liquid–liquid phase separation during solution preparation. Further investigation is always required when the prepared electrolyte has encountered liquid–liquid phase separation previously. Here, we propose a “cognate cosolvent” strategy to mediate phase-separated LiBF₄/fluoroethylene carbonate (FEC)|ethyl trifluoroacetate (TFAE) mixtures with ethyl acetate (EA), forming effective LiBF₄/FEC/EA/TFAE-based LHCEs (B-LHCEs). Because of their unique solvation structure, the B-LHCEs exhibit high oxidative stability, facilitating Li⁺ transport. The optimized B-LHCEs help single-crystal LiMn_0.8Mn_0.1Co_0.1O₂/Li batteries form robust interphases, improving interfacial stability. As a result, distinct performance can be obtained (4.5 V, 500 cycles, ~90%, 1400, ~70%; 25 C, 128 mAh g⁻¹, 4.7 V, 500, 82.5%). This work turns the “impossible” into an “effective” high-voltage electrolyte design, transcending the previous paradigms of electrolyte investigation and enriching LHCE preparation research. Full article

Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) is recognized as a prospective electrode for sodium-ion batteries (SIBs) because of its structure stability, economic viability and environmental friendliness. Nevertheless, its commercialization is constrained by low operating voltage and limited theoretical capacity, which result in a power density significantly inferior to that of LiFePO₄. To address these limitations, in this work, we first designed and synthesized a series of Mn-doped NFPP to enhance its operating voltage, inspired by the successful design of LiFe_1-xMn_xPO₄ cathodes. This approach was implemented to enhance the operating voltage of the material. Subsequently, the optimized Na₄Fe_1.2Mn_1.8(PO₄)₂P₂O₇ (1.8Mn-NFMPP) sample was selected for further Ti-doped modification to enhance its cycle durability and rate performance. The final Mn/Ti co-doped Na₄Fe_1.2Mn_1.7Ti_0.1(PO₄)₂P₂O₇ (0.1Ti-NFMTPP) material exhibited a high operating voltage of ~3.6 V (vs. Na⁺/Na) in a half cell, with an outstanding reversible capacity of 122.9 mAh g⁻¹ at 0.1 C and remained at 90.6% capacity retention after 100 cycles at 0.5 C. When assembled into a coin-type full cell employing a commercial hard carbon anode, the optimized cathode material exhibited an initial capacity of 101.7 mAh g⁻¹, retaining 86.9% capacity retention over 50 cycles at 0.1 C. These results illustrated that optimal Mn/Ti co-doping is an effective methodology to boost the electrochemical behavior of NFPP materials, achieving mitigation of the Jahn–Teller effect on the Mn³⁺ and Mn dissolution problem, thereby significantly improving structural stability and cycling performance. Full article

While 1 M LiPF₆ has been widely adopted as the standard electrolyte in current LIBs, its chemical instability has reduced the battery’s cycling stability by, for instance, accelerating the dissolution of transition metals from electrode materials, particularly in high-voltage cathodes. Lithium bis(fluorosulfonyl)imide (LiFSI) has emerged as a promising alternative salt for next-generation high-voltage energy-dense LIB electrolytes. However, despite extensive research, the optimal concentration and formulation of LiFSI remain unresolved, with variations typically tested across different Li(Ni_1-x-yMn_xCo_y)O₂ (NMC) series cathodes. Herein, 6:4.5:8.3 LiFSI/EC/DMC (in molar ratio) is proposed as a universal electrolyte for high-voltage NMC series cathodes. The 6:4.5:8.3 LiFSI/EC/DMC electrolyte decomposes to form a uniform cathode–electrolyte interface with abundant inorganic species, resulting in a lower interface resistance. By adopting the 6:4.5:8.3 LiFSI/EC/DMC electrolyte, NMC series Li-ion half-cells are all able to stably cycle up to 200 cycles at a cut-off voltage of 4.4 V. Especially for high Ni content (NMC 811) cathode, the capacity retention was improved from 43.6% to 87.5% when charged to 4.4 V at 1C rate. This work provides a feasible universal electrolyte formulation for developing next-generation high-voltage LIBs. Full article

The knowledge of Li diffusivities in electrode materials of Li-ion batteries (LIBs) is essential for a fundamental understanding of charging/discharging times, maximum capacities, stress formation and possible side reactions. The literature indicates that Li diffusion in the cathode material Li(Ni,Mn,Co)O₂ strongly increases during electrochemical delithiation. Such an increased Li diffusivity will be advantageous for performance if it is present already in the initial state after synthesis. In order to understand the influence of a varying initial Li content on Li diffusion, we performed Li tracer diffusion experiments on Li_xCoO₂ (LCO) and Li_xNi_1/3Mn_1/3Co_1/3O₂ (NMC, x = 1, 0.9, 0.65) cathode materials. The measurements were performed on polycrystalline sintered bulk materials, free of additives and binders, in order to study the intrinsic properties. The variation of Li content was achieved using reactive solid-state synthesis using pressed Li₂CO₃, NiO, Co₃O₄ and/or MnO₂ powders and high temperature sintering at 800 °C. XRD analyses showed that the resultant bulk samples exhibit the layered LCO or NMC phases with a low amount of cation intermixing. Moreover, the presence of additional NiO and Co₃O₄ phases was detected in NMC with a pronounced nominal Li deficiency of x = 0.65. As a tracer source, a ⁶Li tracer layer with the same chemical composition was deposited using ion beam sputtering. Secondary ion mass spectrometry in depth profile mode was used for isotopic analysis. The diffusivities followed the Arrhenius law with an activation enthalpy of about 0.8 eV and were nearly identical within error for all samples investigated in the temperature range up to 500 °C. For a diffusion mechanism based on structural Li vacancies, the results indicated that varying the Li content does not result in a change in the vacancy concentration. Consequently, the design and use of a cathode initially made of a Li-deficient material will not improve the kinetics of battery performance. The possible reasons for this unexpected result are discussed. Full article

High-nickel ternary LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) is a promising cathode material for lithium-ion batteries due to its high discharge-specific capacity and energy density. However, problems of NCM622 materials, such as unstable surface structure, lithium–nickel co-segregation, and intergranular cracking, led to a decrease in the cycling performance of the material and an inability to fully utilize high specific capacity. Surface coating was the primary approach to address these problems. The effect of TiO₂ coating prepared by the sol–gel method on the performance of LiNi_0.6Co_0.2Mn_0.2O₂ was studied, mainly including the morphology, cell structure, and electrochemical properties. LiNi_0.6Co_0.2Mn_0.2O₂ was coated by TiO₂ with a thickness of about 5 nm. Compared with the pristine NCM622 electrode, the electrochemical performance of the TiO₂-coated NCM622 electrodes is improved. Among all TiO₂-coated NCM622, the NCM622 cathode with TiO₂ coating content of 0.5% demonstrates the highest capacity retention of 89.3% and a discharge capacity of 163.9 mAh g⁻¹, in contrast to 80.9% and145 mAh g⁻¹ for the pristine NCM622 electrode, after 100 cycles at 0.3 C between 3 and 4.3 V. The cycle life of the 5 wt% TiO₂-coated NCM622 electrode is significantly improved at a high cutoff voltage of 4.6 V. The significantly enhanced cycling performance of TiO₂-coated NCM622 materials could be attributed to the TiO₂ coating layer that could block the contact between the material surface and the electrolyte, reducing the interface side reaction and inhibiting the transition metal dissolution. At the same time, the coating layer maintained the stability of layered structures, thus reducing the polarization phenomenon of the electrode and alleviating the irreversible capacity loss in the cycle process. Full article

Developing highly active and durable non-noble metal catalysts is crucial for energy conversion and storage, especially for proton exchange membrane fuel cells (PEMFCs) and lithium-oxygen (Li-O₂) batteries. Non-noble metal catalysts are considered the greatest potential candidates to replace noble metal catalysts in PEMFCs and Li-O₂ batteries. Herein, we propose a novel type of non-noble metal catalyst (Fe-Hf/N/C) doped with Hf into a mesoporous carbon material derived from Hf-ZIF-8 and co-doping with Fe and N, which greatly enhanced the activity and durability of the catalyst. When applied in the cathode of PEMFCs, the current density can reach up 1.1 and 1.7 A cm⁻² at 0.7 and 0.6 V, respectively, with a maximum power density of 1.15 W cm⁻². The discharge capacity of the Li-O₂ batteries is up to 15,081 mAh g⁻¹ with Fe-Hf/N/C in the cathode, which also shows a lower charge overpotential, 200 mV lower than that of the Fe/N/C. Additionally, the Fe-Hf/N/C catalyst has demonstrated better stability in both PEMFCs and Li-O₂ batteries. This reveals that Hf can not only optimize the electronic structure of iron sites and increase the active sites for the oxygen reduction reaction, but can also anchor the active sites, enhancing the durability of the catalyst. This study provides a new strategy for the development of high-performance and durable catalysts for PEMFCs and Li-O₂ batteries. Full article

The limited rate performance of Li||CF_x batteries hinders their wide application, owing to the low conductivity of CF_x cathode material and the undesirable solid electrolyte interface (SEI) layer formed on the Li anode surface. Herein, a strategy for constructing a three-dimensional lithium anode (3D-Li anode) with high specific surface area and an in situ formed favorable SEI layer is proposed to enhance the interfacial stability and uniformity of ion transport and realize a Li||CF_x battery with remarkable comprehensive performance. A 3D-Li anode (Li@CuO-Cu foam) is successfully constructed by molten Li infusion of a thermal oxidation processed copper foam. The lithiophilicity of the Cu foam framework is optimized by the formed CuO. The Li@CuO-Cu foam||CF_x battery exhibits a high discharge specific capacity (1149.6 mAh g⁻¹ at 0.1 C) along with a high discharge plateau voltage (2.65 V). At a high rate of 10 C, the 3D-Li anode-based batteries still demonstrate a discharge specific capacity of 463 mAh g⁻¹, which is about 2.5 times that of the conventional Li||CF_x, and exhibit excellent storage performance (620.3 mAh g⁻¹ after storage at 55 °C for 90 days) and a low monthly self-discharge rate (1.28%). This work demonstrates a promising strategy to construct a three-dimensional lithium metal anode and significantly improve the rate and storage performance of Li||CF_x batteries. Full article

Due to its high thermal stability, environmental friendliness, and safety, lithium phosphate (Li₃PO₄) is used as a solid electrolyte in battery applications, but it is usually used with dopants due to its lower ionic conductivity, which is required for ion transport. However, due to its stability and environmentally friendly aspect, lithium phosphate is still a hot topic among suitable energy materials that need further research to improve its electrochemical properties. In the current work, a novel synthesis of lithium phosphate was proposed from the raw materials lithium carbonate (Li₂CO₃) and trisodium phosphate dodecahydrate (Na₃PO₄*12H₂O) under suitable stoichiometric conditions using the co-precipitation method. In the set of synthesized samples, a single-phase β-Li₃PO₄ (named LPO-4) with 99.7% purity and 93.49% yield was successfully prepared under appropriate stoichiometric conditions and pH 13 at 90 °C. The average particle size was 10 nm with a large surface area of 9.02 m²g⁻¹. Electrochemical impedance spectroscopy (EIS) of LPO-4 revealed a conductivity of 7.1 × 10⁻⁶ S.cm⁻¹ at room temperature and 2.7 × 10⁻⁵ S.cm⁻¹ at 80 °C with a low activation energy of 0.38 eV. This performance is attributed to the morphology of the nanotubes and the smaller particle size, which enlarge the reaction interfaces and shorten the diffusion distance of lithium ions. The kinetic and thermodynamic key parameters showed that the β-Li₃PO₄ exhibits thermal stability in the room temperature range up to 208.8 °C. All these property values indicate a promising application of lithium phosphate as a solid electrolyte in solid-state batteries and a new route for further investigation. Full article