18 research outputs found

    Surface Chemistry<b>-</b>Controlled SEI Layer on Silicon Electrodes by Regulating Electrolyte Decomposition

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    Unstable solid electrolyte interface (SEI) layers induced by significant volume changes and subsequent side reactions at the interface have prevented Si anodes from practical application in lithium-ion batteries. The interface stability plays an important role in the electrochemical performance of Si electrodes. Here, we modify the interface of a Si electrode with ion-conductive poly(ethylene glycol) diglycidyl ether (PEGDE), which controls the electrolyte decomposition route and stabilizes the SEI layer. It enables the Si electrode to achieve a capacity of more than 1800 mAh g–1 at a current density of 2 A g–1, with a capacity retention of 77.25% after 300 cycles. The PEGDE-decorated Si electrode also shows greatly improved rate capability, with specific capacity up to 777 mAh g–1 even at 20 A g–1. We demonstrate that PEGDE decoration greatly increases the Li2CO3 ratio in the SEI layer, which improves the interface stability and Li+ conductivity and hence suppresses continuous electrolyte decomposition. As a result, the structural integrity of the Si particles is maintained and capacity fading is retarded. This work reveals that surface design can effectively regulate the SEI layer composition and improve interface stability, which is a promising strategy for Si-electrode manufacture

    Tailoring Electrolytes to Enable Low-Temperature Cycling of Ni-Rich NCM Cathode Materials for Li-Ion Batteries

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    The Ni-rich LiNixMnyCozO2 (x + y + z = 1, x > 0.5, Ni-rich NMC) materials are one of the most potential cathodes for high energy density lithium-ion batteries (LIBs) due to their high specific capacity and relatively low cost. However, performances of LIBs with the Ni-rich NCM cathode below 0 °C are restricted by low ion conductivity of the electrolyte and a slow ion diffusion rate at the electrode–electrolyte interphase. Here, γ-butyrolactone (GBL) with a low melting point and high ion conductivity is used to partially replace ethylene carbonate, which is conducive to lower the freezing point and increase the low-temperature ionic conductivity of the electrolyte, and the addition of GBL improves the dissolution of lithium difluoro­(oxalato)­borate (LiDFOB) in a traditional carbonate solvent. Instead of lithium hexafluorophosphate (LiPF6), LiDFOB can form a F-, B-, and O-rich interfacial phase at the Ni-rich NCM cathode, suppressing the fatal interface reaction and reducing the interface impedance. As a result, the electrolyte using GBL as the cosolvent and LiDFOB as the lithium salt can significantly improve the specific discharge capacity and cycling stability of LiNi0.8Co0.1Mn0.1O2/Li cells at 0 °C and −30 °C. At 0 °C, the LiNi0.8Co0.1Mn0.1O2/Li cells have a discharge specific capacity of 160 mA h g–1 and a capacity retention rate of 99% over 100 cycles. They deliver a decent capacity at −30 °C. This rational design of an electrolyte via optimizing the combination of a solvent and a lithium salt has been confirmed to be a low cost but rather an effective method to improve the low-temperature performances of LIBs

    High Chaos Induced Multiple-Anion-Rich Solvation Structure Enabling Ultrahigh Voltage and Wide Temperature Lithium-Metal Batteries

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    The optimal electrolyte for ultrahigh energy density (>400 Wh/kg) lithium-metal batteries with a LiNi0.8Co0.1Mn0.1O2 cathode is required to withstand high voltage (≄4.7 V) and be adaptable over a wide temperature range. However, the battery performance is degraded by aggressive electrode–electrolyte reactions at high temperature and high voltage, while excessive growth of lithium dendrites usually occurs due to poor kinetics at low temperature. Accordingly, the development of electrolytes has encountered challenges in that there is almost no electrolyte simultaneously meeting the above requirements. Herein, a high chaos electrolyte design strategy is proposed, which promotes the formation of weak solvation structures involving multiple anions. By tailoring a Li+-EMC-DMC-DFOB–-PO2F2–-PF6– multiple-anion-rich solvation sheath, a robust inorganic-rich interphase is obtained for the electrode–electrolyte interphase (EEI), which is resistant to the intense interfacial reactions at high voltage (4.7 V) and high temperature (45 °C). In addition, the Li+ solvation is weakened by the multiple-anion solvation structure, which is a benefit to Li+ desolventization at low temperature (−30 °C), greatly improving the charge transfer kinetics and inhibiting the lithium dendrite growth. This work provides an innovative strategy to manipulate the high chaos electrolyte to further optimize solvation chemistry for high voltage and wide temperature applications

    “Room Temperature Molten Salt”-Based Polymer Electrolyte Enabling a High-Rate and High-Thermal Stability Hybrid Li/Na-Ion Battery

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    “Water-in-salt” electrolytes have enlarged the electrochemical window of aqueous electrolytes to 3.0 V. However, the practical application of this electrolyte faces the challenge of high cost. Recently, we have proposed a low-cost inorganic room temperature molten salt (RTMS) electrolyte with a widened electrochemical window of 3.1 V. Herein, the RTMS electrolyte has been integrated with a hydrophilic polymer by ultrafast polymerization through electron beam irradiation to further enlarge the anode limit, increase the ionic conductivity, and improve the thermal stability. The double-redox-active Prussian blue analogues of the cobalt hexacyanoferrate cathode (NaCoHCF) in the RTMS-based polymer electrolyte prepared by electron beam (EB) irradiation (e-RPE) show electrochemical performance with a high capacity of 137 mAh·g–1 at 1C and 100 mAh·g–1 at 5C. More significantly, at a high temperature of 60 °C, the NaCoHCF electrode in e-RPE exhibits a high capacity of 120 mAh·g–1 at 5C and a high capacity retention of 92% over 100 cycles at 1C. Compared to RTMS, the RTMS-based polymer electrolyte not only expands the hydrogen evolution limit but also shows high thermal stability, which is favorable for the electrochemical performance of NaCoHCF at high temperature. Furthermore, the battery with e-RPE is intrinsically safe and can be widely used in large-scale energy storage and wearable device applications

    Electrolyte Salts for Sodium-Ion Batteries: NaPF<sub>6</sub> or NaClO<sub>4</sub>?

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    NaClO4 and NaPF6, the most universally adopted electrolyte salts in commercial sodium-ion batteries (SIBs), have a decisive influence on the interfacial chemistry, which is closely related to electrochemical performance. The complicated and ambiguous interior mechanism of microscopic interfacial chemistry has prevented reaching a consensus regarding the most suitable sodium salt for high-performance SIB electrolytes. Herein, we reveal that the solvation structure induced by different sodium salt anions determines the Na+ desolvation kinetics and interfacial film evolution process. Specifically, the weak interaction between Na+ and PF6– promoted sodium desolvation and storage kinetics. The solvation structure involving PF6– induced the anion’s preferential decomposition, generating a thin, inorganic compound–rich cathode–electrolyte interphase that ensured interface stability and inhibited solvent decomposition, thereby guaranteeing electrode stability and promoting the charge transfer kinetics. This study provides clear evidence that NaPF6 is not only more compatible with industrial processes but also more conducive to battery performance. Commercial electrolyte design employing NaPF6 will undoubtedly promote the industrialization of SIBs

    Image_1_Enhanced pathogenicity by up-regulation of A20 after avian leukemia subgroup a virus infection.TIF

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    Avian leukemia virus subgroup A (ALV-A) infection slows chicken growth, immunosuppression, and tumor occurrence, causing economic loss to the poultry industry. According to previous findings, A20 has a dual role in promoting and inhibiting tumor formation but has rarely been studied in avians. In this study, A20 overexpression and shRNA interference recombinant adenoviruses were constructed and inoculated into chicken embryos, and ALV-A (rHB2015012) was inoculated into 1-day-old chicks. Analysis of body weight, organ index, detoxification, antibody production, organ toxin load, and Pathological observation revealed that A20 overexpression could enhance ALV-A pathogenicity. This study lays the foundation for subsequent exploration of the A20-mediated tumorigenic mechanism of ALV-A.</p

    Image_2_Enhanced pathogenicity by up-regulation of A20 after avian leukemia subgroup a virus infection.TIF

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    Avian leukemia virus subgroup A (ALV-A) infection slows chicken growth, immunosuppression, and tumor occurrence, causing economic loss to the poultry industry. According to previous findings, A20 has a dual role in promoting and inhibiting tumor formation but has rarely been studied in avians. In this study, A20 overexpression and shRNA interference recombinant adenoviruses were constructed and inoculated into chicken embryos, and ALV-A (rHB2015012) was inoculated into 1-day-old chicks. Analysis of body weight, organ index, detoxification, antibody production, organ toxin load, and Pathological observation revealed that A20 overexpression could enhance ALV-A pathogenicity. This study lays the foundation for subsequent exploration of the A20-mediated tumorigenic mechanism of ALV-A.</p

    Entropy-Driven Enhancement of the Conductivity and Phase Purity of Na<sub>4</sub>Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>P<sub>2</sub>O<sub>7</sub> as the Superior Cathode in Sodium-Ion Batteries

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    Na4Fe3(PO4)2(P2O7) (NFPP) is regarded as a promising cathode material for sodium-ion batteries (SIBs) owing to its low cost, easy manufacture, environmental purity, high structural stability, unique three-dimensional Na-ion diffusion channels, and appropriate working voltage. However, for NFPP, the low conductivity of electrons and ions limits their capacity and power density. The generation of NaFeP2O7 and NaFePO4 inhibits the diffusion of sodium ions and reduces reversible capacity and rate performance during the manufacturing process in synthesis methods. Herein, we report an entropy-driven approach to enhance the electronic conductivity and, concurrently, phase purity of NFPP as the superior cathode in sodium-ion batteries. This approach was realized via Ti ions substituting different ratios of Fe-occupied sites in the NFPP lattice (denoted as NTFPP-X, T is the Ti in the lattice, X is the ratio of Ti-substitution) with the configurational entropic increment of the lattice structures from 0.68 R to 0.79 R. Specifically, 5% Ti-substituted lattice (NTFPP-0.05) inducing entropic augmentation not only improves the electronic conductivity from 7.1 × 10–2 S/m to 8.6 × 10–2 S/m but also generates the pure-phase of NFPP (suppressing the impure phases of the NaFeP2O7 and NaFePO4) of the lattice structure, which is validated by a series of characterizations, including powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Benefiting from the Ti replacement in the lattice, the optimal NTFPP-0.05 composite shows a high first discharge capacity (118.5 mAh g–1 at 0.1 C), superior rate performance (70.5 mAh g–1 at 10 C), and excellent long cycling life (1200 cycles at 10 C with capacity retention of 86.9%). This research proposes a new entropy-driven approach to improve the electrochemical performance of NFPP and reports a low-cost, ultrastable, and high-rate cathode material of NTFPP-0.05 for SIBs

    Engineering Nanoparticle-Coated Bacteria as Oral DNA Vaccines for Cancer Immunotherapy

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    Live attenuated bacteria are of increasing importance in biotechnology and medicine in the emerging field of cancer immunotherapy. Oral DNA vaccination mediated by live attenuated bacteria often suffers from low infection efficiency due to various biological barriers during the infection process. To this end, we herein report, for the first time, a new strategy to engineer cationic nanoparticle-coated bacterial vectors that can efficiently deliver oral DNA vaccine for efficacious cancer immunotherapy. By coating live attenuated bacteria with synthetic nanoparticles self-assembled from cationic polymers and plasmid DNA, the protective nanoparticle coating layer is able to facilitate bacteria to effectively escape phagosomes, significantly enhance the acid tolerance of bacteria in stomach and intestines, and greatly promote dissemination of bacteria into blood circulation after oral administration. Most importantly, oral delivery of DNA vaccines encoding autologous vascular endothelial growth factor receptor 2 (VEGFR2) by this hybrid vector showed remarkable T cell activation and cytokine production. Successful inhibition of tumor growth was also achieved by efficient oral delivery of VEGFR2 with nanoparticle-coated bacterial vectors due to angiogenesis suppression in the tumor vasculature and tumor necrosis. This proof-of-concept work demonstrates that coating live bacterial cells with synthetic nanoparticles represents a promising strategy to engineer efficient and versatile DNA vaccines for the era of immunotherapy
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