High lithium ionic conductivity and stability against lithium metal of solid electrolytes are crucial to develop high energy density all-solid-state lithium batteries. Upon doping LiI in Li3PS4, the ...low temperature phase Li7P2S8I glass-ceramic electrolyte (LT-Li7P2S8I) can be synthesized by mechanical milling followed by heat treatment. Compared with Li3PS4, the obtained LT-Li7P2S8I shows a phase transition from low conductive thio-LISICON III analog to high conductive thio-LISICON II analog phase, exhibiting a favorable conductivity of 1.57 × 10−3 S cm−1 at room temperature. In addition, the as-prepared LT-Li7P2S8I possesses excellent dendrite suppression capability and compatibility with lithium metal. The Li/LT-Li7P2S8I/Li symmetric cell demonstrates long cycling stability for 2400 h at 0.2 mA cm−2. As a result, LiCoO2/LT-Li7P2S8I/Li all-solid-state battery delivers an initial discharge capacity of 115 mAh g−1 at 0.1 C and high capacity retention of 93% after 100 cycles at room temperature. Moreover, the obtained all-solid-state battery also shows improved rate capacity. This work provides a promising electrolyte with high ionic conductivity and stability against lithium for all-solid-state lithium batteries.
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•The low temperature phase Li7P2S8I is synthesized by doping LiI in Li3PS4.•The low temperature phase Li7P2S8I shows high conductivity of 1.57 × 10−3 S cm−1.•LT-Li7P2S8I electrolyte possesses outstanding stability against lithium.•LiCoO2/LT-Li7P2S8I/Li battery shows excellent cycling stability and rate capability.
The instability of Li10GeP2S12 toward moisture and that toward lithium metal are two challenges for the application in all‐solid‐state lithium batteries. In this work, Li10GeP2S12 is fluorinated to ...form a LiF‐coated core–shell solid electrolyte LiF@Li10GeP2S12. Density‐functional theory calculations confirm the hydrolysis mechanism of Li10GeP2S12 solid electrolyte, including H2O adsorption on Li atoms of Li10GeP2S12 and the subsequent PS43− dissociation affected by hydrogen bond. The hydrophobic LiF shell can reduce the adsorption site, thus resulting in superior moisture stability when exposing in 30% relative humidity air. Moreover, with LiF shell, Li10GeP2S12 shows one order lower electronic conductivity, which can significantly suppress lithium dendrite growth and reduce the side reaction between Li10GeP2S12 and lithium, realizing three times higher critical current density to 3 mA cm−2. The assembled LiNbO3@LiCoO2/LiF@Li10GeP2S12/Li battery exhibits an initial discharge capacity of 101.0 mAh g−1 with a capacity retention of 94.8% after 1000 cycles at 1 C.
LiF‐coated core–shell electrolyte LiF@Li10GeP2S12 is achieved by in situ gas‐phase fluoridation. Benefiting from the LiF shell, LiF@Li10GeP2S12 exhibits excellent compatibility toward moisture and lithium metal, realizing a high ionic conductivity after air exposure and three times higher critical current density. The assembled all‐solid‐state lithium battery exhibits a capacity retention of 94.8% after 1000 cycles at 1 C.
All-solid-state lithium-sulfur batteries can completely overcome safety issues and fast capacity fading by substitution of organic liquid electrolytes and eliminating polysulfide shuttle. However, ...the insulating nature of sulfur and large volume change still inhibit all-solid-state lithium-sulfur batteries from achieving favorable electrochemical performances. In this work, linear-chain compound vanadium tetrasulfide (VS4) anchored reduced graphene oxide (rGO-VS4) nanocomposites are successfully synthesized via a simple one-pot hydrothermal method. Furthermore, 10%rGO-VS4@Li7P3S11 nanocomposites with multi-channel continuous electronic/ionic conductive network are prepared by a facile liquid-phase deposition reaction and further employed as an alternative material for sulfur cathode in all-solid-state lithium batteries. Typically, Li/75%Li2S-24%P2S5-1%P2O5/Li10GeP2S12/10%rGO-VS4@Li7P3S11 all-solid-state lithium-sulfur batteries deliver high reversible capacity of 611 mAh g−1 at 0.1 A g−1 after 100 cycles, corresponding to 853 mAh g−1 based on the mass of sulfur. Even after being cycled at 0.5 A g−1 between 1.5 and 3.0 V for 500 cycles, it still shows the discharge specific capacity of 333 mAh g−1 based on sulfur content with excellent cycling stability. The excellent rate capability and cycle performances can be ascribed to the multi-channel continuous electronic/ionic conductive networks and the improved structural stability. In addition, the electrochemical reaction kinetics and capacity contributions as well as reaction mechanisms of 10%rGO-VS4@Li7P3S11 in all-solid-state lithium batteries were revealed by ex-situ characterization techniques.
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•The 10%rGO-VS4@Li7P3S11 is employed as an alternative electrode for sulfur.•The unique structures enhance ionic/electronic conductions and structural stability.•Room-temperature all-solid-state Li-S cells show superior rate and cyclic performances.•The reaction mechanisms are revealed via ex-situ characterization.
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•Na10SnSb2S12 with nanoscale particle size is synthetized by liquid phase process.•Na10SnSb2S12 shows ion conductivity of 0.52 mS cm−1.•Excellent air stability is achieved by ...replacing phosphorus with antimony.•All-solid-state sodium batteries display excellent cycling stability and rate capability.
All-solid-state sodium batteries are attractive for large-scale energy storage due to their low cost, wide variety of cathode materials and high safety. And sulfide sodium solid electrolytes are key to enable room-temperature all-solid-state sodium batteries. Herein, we report the quaternary nanosized solid electrolyte Na10SnSb2S12 synthetized through liquid phase process. The crystalline structure and diffusion path of Na10SnSb2S12 are investigated through the first principles calculations. The Na10SnSb2S12 electrolyte presents a room temperature conductivity of 0.52 mS cm−1 at 25 °C and very low activation energy of 0.23 eV as well as excellent air stability by replacing phosphorus with antimony. Moreover, the small particle size of the solid electrolytes enhances the contact between solid electrolyte and electrode, reducing the interfacial contact resistance. Consequently, the TiS2/Na10SnSb2S12/Na all-solid-state sodium batteries show excellent cycling stability and exhibit a capacity of 119.6 mAh g−1 after cycling for 100 cycles at 100 mA g−1.
All-solid-state batteries can enable reversible four lithium ion storage for pyrite (FeS2) at a cutoff voltage of 1.0–3.0 V. However, strain/stress concentration generating electrode pulverization ...and sluggish electrochemical reaction of lithium sulfide and sulfur will affect the long cycling stability of the battery. Through experiments and density functional theory (DFT) calculations, it is proved that nanostructure engineering and electronic conduction improvement with introduction of catalytic cobalt can effectively improve the electrochemical activity of FeS2. The optimized loose structured Co0.1Fe0.9S2 based all-solid-state lithium batteries show reversible capacities of 860.5, 797.7, 685.8, and 561.8 mAh g–1 after five cycles at 100, 200, 500, and 1000 mA g–1, respectively, and a stable capacity of 543.5 mAh g–1 can be maintained after cycling at a current density of 500 mA g–1 for 100 cycles. Ex situ TEM and Raman results reveal that, after the first cycle, the reversible reaction 2Li2S + Fe ↔ FeS y + (2 – y)S + 4Li+ + 4e – proceeds from the following cycles onward, while nanocrystalline mackinawite FeS, Fe(III)-containing mackinawite FeS, and Fe3S4 are generated after the first discharge–charge process. This work provides a facile method for improving the electrochemical performance for multi-electron reaction mechanism based all-solid-state lithium batteries.
Rheumatoid arthritis (RA) is a chronic inflammatory disease. Abnormal proliferation and inflammation of fibroblast-like synoviocytes (FLSs) are the main pathological features of the disease. ...Accumulating studies have identified that circular RNAs (circRNAs) were involved in the progression of RA. Our study was to assess the function and mechanism of circ_0083964 in RA.
Quantitative real-time polymerase chain reaction (qRT-PCR) and western blot were utilized to test the level of circ_0083964, miR-204-5p and YY1. Counting Kit-8 (CCK-8) assay, EdU assay, flow cytometry, transwell assay and wound-healing assay were utilized to test cell viability, proliferation, apoptosis, invasion and migration. Cell inflammation was estimated with enzyme-linked immunosorbent assay (ELISA) kits. Dual-luciferase reporter assay and RNA immunoprecipitation (RIP) assay were employed to identify the target relationship between miR-204-5p and circ_0083964 or YY1.
Circ_0083964 was highly expressed in RA synovial tissues and RA-FLSs. Circ_0083964 downregulation constrained proliferation, metastasis and inflammation and facilitated apoptosis in RA-FLSs. Furthermore, circ_0083964 served as a sponge of miR-204-5p, and rescue experiments proved that miR-204-5p deficiency overturned the suppressive impacts of circ_0083964 silencing on RA-FLSs progression. Additionally, we also verified that YY1 could be targeted by miR-204-5p, and its overexpression rescued the repressive impact of miR-204-5p introduction on RA-FLSs development. Besides that, we revealed that circ_0083964 mediated YY1 expression by regulating miR-204-5p.
Circ_0083964 inhibition confined RA development by sponging miR-204-5p to hamper the YY1 level, which will provide a theoretical basis for the treatment of RA.
Sulfide solid electrolyte membranes employed in all-solid-state lithium batteries generally show high thickness and poor chemical stability, which limit the cell-level energy density and cycle life. ...In this work, Li9.88GeP1.96Sb0.04S11.88Cl0.12 solid electrolyte is synthesized with Sb, Cl partial substitution of P, S, possessing excellent toluene tolerance and stability to lithium. The formed SbS4 3– group in Li9.88GeP1.96Sb0.04S11.88Cl0.12 exhibits low adsorption energy and reactivity for toluene molecules, confirmed by first-principles density functional theory calculation. Using toluene as the solvent, ultrathin Li9.88GeP1.96Sb0.04S11.88Cl0.12 membranes with adjustable thicknesses can be well prepared by the wet coating method, and an 8 μm thick membrane exhibits an ionic conductivity of 1.9 mS cm–1 with ultrahigh ionic conductance of 1860 mS and ultralow areal resistance of 0.68 Ω cm–2 at 25 °C. The obtained LiCoO2|Li9.88GeP1.96Sb0.04S11.88Cl0.12 membrane|Li all-solid-state lithium battery shows an initial reversible capacity of 125.6 mAh g–1 with a capacity retention of 86.3% after 250 cycles at 0.1 C under 60 °C.
Three dimensional abundant Ge nanocoatings anodes were successfully constructed on the patterned Si substrate and displayed improved electrochemical performance in Li ion microbatteries.
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•The three dimensional (3D) Si@hedgehog-like (Si@H-Ge) NRs composites anodes embrace improved Li ion storage ability.•The 3D hedgehog-like Ge shell nanoelectrodes provide an efficient pathway for ion/electron transport during cycling.•The abundant of the unique Ge nanocoatings may open up a new way to improve the electrochemical performance of other Si based Li ion microbatteries.
Three dimensional (3D) hedgehog-like Ge nanoelectrodes coated on patterned Si substrate are successfully fabricated through the facile chemical vapor deposition (CVD) process. The 3D Si substrate with enlarged surface area and the abundant Ge shell electrode configuration are together favorable to enhance the lithiation/delithiation kinetics during cycling. Impressively, the optimized 3D Si@hedgehog-like Ge (Si@H-Ge) NRs composites anodes embrace high reversible areal capacity and superior rate capability when employed as anode material for 3D Si based lithium ion microbatteries (LIMBs).
The nanosized Na11Sn2PS12 solid electrolyte with a particle size of around 200 nm is synthesized using the liquid-phase method using 1,2-dimethoxyethane. The sintering conditions for Na11Sn2PS12 ...crystallization are systematically optimized to maximize ionic conductivity. The highest room temperature ionic conductivity of the liquid-phase-synthesized Na11Sn2PS12 electrolytes (LP-Na11Sn2PS12) is 1.73 × 10–4 S cm–1, which is comparable with that of ball-milling samples (BM-Na11Sn2PS12) of 2.16 × 10–4 S cm–1. Both Na11Sn2PS12 electrolytes show an electrochemical window of 0.3–3.2 V. Moreover, the as-synthesized Na11Sn2PS12 electrolytes are employed as solid electrolytes in TiS2/Na11Sn2PS12/Na all-solid-state batteries. The TiS2/LP-Na11Sn2PS12/Na battery shows a higher reversible capacity of 142.4 mAh g–1 compared with 110.5 mAh g–1 for the TiS2/BM-Na11Sn2PS12/Na battery after 10 cycles under 20 mA g–1 at 25 °C. The better performance of the TiS2/LP-Na11Sn2PS12/Na battery can be ascribed to improved solid–solid contact between the electrolyte and the electrode arising from the nanosized particles of LP-Na11Sn2PS12 electrolytes.
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